CN109225291A - A kind of Ti3C2Compound transition-metal catalyst of-FeOOH and its preparation method and application - Google Patents
A kind of Ti3C2Compound transition-metal catalyst of-FeOOH and its preparation method and application Download PDFInfo
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- CN109225291A CN109225291A CN201811053532.6A CN201811053532A CN109225291A CN 109225291 A CN109225291 A CN 109225291A CN 201811053532 A CN201811053532 A CN 201811053532A CN 109225291 A CN109225291 A CN 109225291A
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- 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
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- 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
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention discloses a kind of Ti3C2Compound transition-metal catalyst of-FeOOH and its preparation method and application provides a kind of method for being catalyzed the preparation method and degradable organic pollutant of the composite metal hydroxide catalyst of PMS degradation organic pollutants.The metallic catalyst is with Ti3C2It is raw material with etal molysite, is configured to mixed solution, is prepared by hydro-thermal method containing Ti3C2With the compound transition-metal catalyst of FeOOH.Appropriate oxidant permonosulphuric acid hydrogen salt (PMS) is added into organic pollutant solution and the compound transition-metal catalyst of the present invention carries out the reaction of catalytic degradation organic pollutant.Compound technology catalyst degradable organic pollutant effect of the invention is good, and degradation rate is high, and method is simple, has achieved the purpose that efficient pollution treatment.
Description
Technical field
The present invention relates to the technical fields of organic catalyst preparation, and in particular to a kind of Ti3C2The compound transition gold of-FeOOH
Metal catalyst and its preparation method and application, catalyst prepared by the present invention is for organic in permonosulphuric acid hydrogen salt oxygenolysis water
Pollutant has good catalytic performance, and possesses preferable repeatability, is suitable for embryonic stem-like cells.
Background technique
The development of chemical industry is maked rapid progress, but the waste water given off is largely that complicated component, concentration is higher, difficult life
The substance of object degradation, brings harm to ecological environment and human health, and traditional wastewater treatment method is for this substance
Removal effect it is unsatisfactory.In recent decades, high-level oxidation technology (Advanced Oxidation Technologies,
AOTs) because the high efficiency of its degradable organic pollutant has obtained domestic and foreign scholars' extensive concern, it is using raw in reaction process
At strong oxidizing property free radical (such as: OH, OOH) organic contamination is degraded into small-molecule substance, be finally mineralized into CO2、
H2O and corresponding inorganic ions.In various high-level oxidation technologies, Fenton oxidation method is because of its easy to operate, low-cost, nothing
Must complex device and it is environmentally friendly the advantages that have received more concern, and gradually developed light help Fenton, Fenton,
The Fenton system such as photoelectro-Fenton process.But Fenton oxidation method also has its apparent limitation, comprising: (1) reaction is in pH value
Just there is greater activity close under conditions of 3；(2) reaction process will generate a large amount of sludge due to iron aggregation and sedimentation；(3) it needs to disappear
Consume a large amount of chemical reagent, especially expensive H2O2；(4) iron catalytic efficiency is low, and catalysis is slow, and the dosage of molysite is very high,
Real catalytic action is not played；(5) expected degradation effect is unable to reach to some organic matters, TOC removal rate is no more than
60%.
To overcome many limitations existing for Fenton oxidation method, in recent years, many scholars are had studied and Fenton oxidation method
Similar system: " transition metal+peroxide ", such as Ni (II)/permonosulphuric acid hydrogen salt (peroxymonosulfate, PMS)
System, Ag (I)/PMS system etc..1956, Ball and Edwards, which report cobalt for the first time PMS generation can be catalytically decomposed, to be had
The free radical of enhanced type.Know 2003, the Anipsitakis of Ohio State Univ-Columbus USA is just for the first time by this advanced oxidation skill
Art is applied in field of waste water treatment.Oxone is to provide the product name of active ingredient substance PMS, alias: permonosulphuric acid hydrogen salt,
Chemical composition are as follows: 2KHSO5·KHSO4·K2SO4, standard oxidationreduction potential E0=+1.82V (relative to standard hydrogen electrode,
Similarly hereinafter), it is higher than H2O2(E0=+1.76V), have many advantages, such as that property is stable, be easily handled, be nontoxic and low in cost, is a kind of
Stronger oxidant.PMS is different from other oxidants (such as H2O2、K2S2O8Deng), it is one and the army of HOOH is replaced to groan peroxide
Compound, its own unique texture make itself to be easy to be excited and activate.Studies have shown that variable valency metal ions M2+And oxidation
Object MOX(wherein x=1,2,3, M represent Co, Mn, Cu, Ce and Fe etc.) all there is activation PMS to generate active ability, with
Fenton reaction system compares, its biggest advantage is that (3-10) can keep higher oxidation activity at a wider pH range,
And the dosage of catalyst is seldom, and oxidation removal organic matter reaction equation can be expressed as follows:
M2++HSO- 5→M3++SO2 4 -+OH-
SO2 4 -+organics→[…many steps…]→CO2+H2O
Although homogeneous M2+/ PMS has the advantages that high catalytic efficiency, oxidability by force, but there is also catalyst to recycle
It utilizes, there are trace metal ion difficulties in solution separates with reaction medium, is likely to result in potential secondary pollution and biology poison
The problems such as property.If can lose activity by metal ion immobilization, and not, then above disadvantage can be obtained by gram
Clothes.
Transition metal hydroxide removes water pollutant for catalytic oxidation technique as catalyst, is to come more this year
Concerned new method/due to transition metal hydroxide have the characteristics that surface hydroxyl it is intensive, without oxidizable dentate.
It can be used in catalysis oxidation water treatment procedure.Simultaneously because alpha-feooh is prevalent in nature, the side of alpha-feooh is prepared
Method multiplicity, simple and cost is relatively low, so the research about alpha-feooh catalysis oxidation water pollutant is more.
At the same time, Ti3C2As a kind of novel two-dimensional material, there is excellent catalytic action, and can also be used as
The reinforced phase of composite material, therefore, by alpha-feooh and Ti3C2It is compound to be just able to solve the above problem, utilize the compound of the two
It is also feasible for activating PMS degradation organic pollutants.
It can be obtained according to data, iron and Ti3C2There is a synergy between, and the two doping can effectively improve catalytic activity.
Therefore, iron is used for Fenton, embryonic stem-like cells degradable organic pollutant has great significance to the depollution of environment.
Summary of the invention
Goal of the invention: to overcome the deficiencies in the prior art described above, the present invention is intended to provide a kind of Ti3C2- FeOOH is multiple
Mould assembly transition-metal catalyst and its preparation method and application, the application are mainly used for degradable organic pollutant.The present invention is compound
Type transition-metal catalyst catalytic degradation organic pollutant effect is good, and degradation rate is high, and solid-phase catalyst digestion of metallic ion is low,
It is easily isolated, it is low in cost, provide a kind of pollution treatment new technology.
The present invention is with Ti3C2, transition metal is prepared compound transition-metal catalyst, and by itself and hydrogen peroxymonosulfate
Salt combines, and constitutes the new advanced oxidation system of one kind with degradable organic pollutant.Compound transition metal prepared by the present invention
Transition metal and Ti in catalyst3C2Has the function of concerted catalysis, energy synergistic activation PMS generates active sulfate radical certainly
It, can more quick degradable organic pollutant by base.
Technical solution: in order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of Ti3C2- FeOOH is multiple
The preparation method of mould assembly transition-metal catalyst, comprising the following steps:
1) by Ti3C2It is added to the water, carries out ultrasound, it is made to be uniformly dispersed to obtain solution 1；
2) FeCl will be contained3·6H2The solution of O is added dropwise in solution 1, and 20~40min of magnetic agitation obtains solution 2；
3) under conditions of 170~190 DEG C, solution 2 is carried out to obtain solid after hydro-thermal method heats 23~25h filtering；
4) the obtained solid of step 3) is washed with deionized, then dries 12h under conditions of 50~70 DEG C to obtain the final product
To Ti3C2The compound transition-metal catalyst of-FeOOH.
It wherein, is ultrapure water described in step 1).
Wherein, the speed of agitator of the step 2) is 200~400rpm.
Wherein, the step 2) FeOOH and Ti3C2Mass ratio be 1:3~1:4.
The content of present invention further includes Ti made from the preparation method3C2The compound transition-metal catalyst of-FeOOH.
The content of present invention further includes the Ti3C2The compound transition-metal catalyst of-FeOOH is in organic pollutant degradation
In application.
The content of present invention further includes a kind of method of degradable organic pollutant, by the Ti3C2The compound transition of-FeOOH
Metallic catalyst degradable organic pollutant in conjunction with permonosulphuric acid hydrogen salt.
Wherein, the method for a kind of degradable organic pollutant, specifically includes the following steps: to organic pollutant solution
Middle addition oxidant permonosulphuric acid hydrogen salt and Ti3C2The compound transition-metal catalyst of-FeOOH, so that permonosulphuric acid hydrogen salt is dense
Degree is 0.1-0.8g/L, Ti3C2The concentration of-FeOOH composite metallic catalyst is 0.1-1g/L, pH=3-9,25-45 DEG C of stirring
Reaction 3 hours complete to organic pollutant degradation.
Wherein, the organic pollutant is salicylic acid, and the organic pollutant solution concentration is 10~80mg/L.
Wherein, the oxidant permonosulphuric acid hydrogen salt, Ti3C2- FeOOH composite metallic catalyst and organic pollutant
Mass ratio is 5-40:5-50:1.
The compound transition-metal catalyst of the present invention can activate PMS to generate the potentiometric titrations with catalytic activity, and
Potentiometric titrations can make organic pollutant that degradation reaction, mineralising CO occur2And H2O；Wherein Ti3C2With catalytic activity,
Play the role of Synergistic degradation.
Specific step is as follows for degradable organic pollutant of the present invention:
The organic pollutant solution that concentration is 20mg/L is placed in heterogeneous activated reactor by A；
The compound transition-metal catalyst of the present invention is added into reactor by B, so that compound transition-metal catalyst
Concentration is 0.1-1g/L, is sufficiently stirred；
Oxidant PMS is added into reactor by C, so that the concentration of oxidant is 0.1-0.8g/L；
D, which is sufficiently mixed, to be stirred to react until organic pollutant mineralising is complete.
The utility model has the advantages that compared with the existing technology, the present invention has following advantage: Ti of the invention3C2The compound mistake of-FeOOH
Metallic catalyst is crossed in conjunction with permonosulphuric acid hydrogen salt, advanced oxidation technical system is constituted, organic pollutant has been reached very
Good removal effect, and solid-phase catalyst digestion of metallic ion is low, is easily isolated；Process flow is simple, at low cost, has fine
Actual application prospect.
Detailed description of the invention
Fig. 1 is embodiment 5 using compound transition metal as the salicylic degradation efficiency of Fenton's reaction catalyst degradation
Figure.It can be seen from the figure that salicylic degradation rate is more than 90% at 120 minutes, illustrates that it degrades in organic contamination and be catalyzed
In application.
Fig. 2 is the Ti being prepared3C2SEM (scanning electron microscope) photo of the compound transition-metal catalyst of-FeOOH.From figure
In as can be seen that the catalyst that is prepared in organ shape, Ti3C2It is tightly combined with alpha-feooh.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Embodiment 1
1, the preparation of composite catalyst
By 0.8gTi3C2It is added in 50mL water, carries out ultrasound, it is made to be uniformly dispersed；2mL is then contained 0.608g's
FeCl3·6H20 solution is added dropwise in above-mentioned solution；Then by above-mentioned solution magnetic agitation 30min, speed of agitator is
300rpm；Finally under conditions of 180 DEG C, above-mentioned solution is carried out to obtain solid after hydro-thermal method heating is filtered for 24 hours, uses deionization
The obtained solid of water washing dries 12h under conditions of 60 DEG C then up to compound transition-metal catalyst.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL, pH=3), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, in 25 DEG C of constant temperature
It is reacted 3 hours under water-bath, organic pollutant degradation rate can reach 100%.
Embodiment 2
1, the preparation of composite catalyst
By 0.8gTi3C2It is added in 50mL water, carries out ultrasound, it is made to be uniformly dispersed；2mL is then contained into FeCl3·
6H20 solution is added dropwise in above-mentioned solution, so that FeOOH and Ti3C2Mass ratio be 1:3；Then by above-mentioned solution
Magnetic agitation 20min, speed of agitator 200rpm；Finally under conditions of 170 DEG C, hydro-thermal method heating is carried out to above-mentioned solution
Solid is obtained after 23h filtering, obtained solid is washed with deionized, then dry 12h under the conditions of 50 DEG C.Up to compound
Type transition-metal catalyst.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL, pH=6), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, in 25 DEG C of constant temperature
It is reacted 3 hours under water-bath, organic pollutant degradation rate can reach 97.4%.
Embodiment 3
1, the preparation of composite catalyst
By 0.8gTi3C2It is added in 50mL water, carries out ultrasound, it is made to be uniformly dispersed；2mL is then contained into FeCl3·
6H20 solution is added dropwise in above-mentioned solution, so that FeOOH and Ti3C2Mass ratio be 2:7；Then by above-mentioned solution
Magnetic agitation 40min, speed of agitator 400rpm；Finally under conditions of 190 DEG C, hydro-thermal method heating is carried out to above-mentioned solution
Solid is obtained after 25h filtering, obtained solid is washed with deionized, then dry 12h under the conditions of 70 DEG C.Up to compound
Type transition-metal catalyst.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL, pH=9), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, in 25 DEG C of constant temperature
It is reacted 3 hours under water-bath, organic pollutant degradation rate can reach 89.5%.
Embodiment 4
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 10mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 95.3%.
Embodiment 5
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 98.7%.
Embodiment 6
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 50mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 100%.
Embodiment 7
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 80mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 100%.
Embodiment 8
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 10mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 97.9%.
Embodiment 9
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 50mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 98.2%.
Embodiment 10
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 100mg of step 1 preparation is weighed, the salicylic acid that the 20mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 98.4%.
Embodiment 11
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 10mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 100%.
Embodiment 12
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 50mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 98.5%.
Embodiment 13
1, the preparation of composite catalyst
The preparation method of compound transition-metal catalyst is such as embodiment 1 in the present embodiment.
2, the degradation of organic pollutant
The compound transition-metal catalyst of 20mg of step 1 preparation is weighed, the salicylic acid that the 80mg/L prepared is added is molten
Liquid simulative organic wastewater (V=100mL), while oxidant permonosulphuric acid hydrogen salt (PMS) 20mg is added, under 25 DEG C of waters bath with thermostatic control
Reaction 3 hours, organic pollutant degradation rate can reach 97.3%.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (9)
1. a kind of Ti3C2The preparation method of the compound transition-metal catalyst of-FeOOH, which comprises the following steps:
1) by Ti3C2It is added to the water, carries out ultrasound, it is made to be uniformly dispersed to obtain solution 1；
2) FeCl will be contained3·6H2The solution of O is added dropwise in solution 1, and 20 ~ 40min of magnetic agitation obtains solution 2；
3) under conditions of 170 ~ 190 DEG C, solution 2 is carried out solid is obtained by filtration after hydro-thermal method heats 23 ~ 25h；
4) the obtained solid of step 3) is washed with deionized, dries 12h under conditions of 50 ~ 70 DEG C then to get arriving
Ti3C2The compound transition-metal catalyst of-FeOOH.
2. a kind of Ti according to claim 13C2The preparation method of the compound transition-metal catalyst of-FeOOH, feature exist
In the speed of agitator of the step 2 is 200 ~ 400rpm.
3. a kind of Ti according to claim 13C2The preparation method of the compound transition-metal catalyst of-FeOOH, feature
It is, the step 2 FeOOH and Ti3C2Mass ratio be 1:3 ~ 1:4.
4. Ti made from the described in any item preparation methods of claim 1 ~ 33C2The compound transition-metal catalyst of-FeOOH.
5. Ti as claimed in claim 43C2Application of the compound transition-metal catalyst of-FeOOH in organic pollutant degradation.
6. a kind of method of degradable organic pollutant, which is characterized in that by Ti as claimed in claim 43C2The compound mistake of-FeOOH
Cross metallic catalyst degradable organic pollutant in conjunction with permonosulphuric acid hydrogen salt.
7. a kind of method of degradable organic pollutant according to claim 6, which comprises the following steps: to
Oxidant permonosulphuric acid hydrogen salt and Ti are added in organic pollutant solution3C2The compound transition-metal catalyst of-FeOOH, so that mistake
The concentration of one disulfate is 0.1-0.8g/L, Ti3C2The concentration of-FeOOH composite metallic catalyst is 0.1-1g/L, pH=3-
9,25-45 DEG C be stirred to react 3 hours it is complete to organic pollutant degradation.
8. a kind of method of degradable organic pollutant according to claim 5, which is characterized in that the organic pollutant is
Salicylic acid, the organic pollutant solution concentration are 10 ~ 80mg/L.
9. a kind of method of degradable organic pollutant according to claim 7, which is characterized in that the oxidant crosses a sulphur
Sour hydrogen salt, Ti3C2The mass ratio of-FeOOH composite metallic catalyst and organic pollutant is 5-40:5-50:1.
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| CN112517035A (en) * | 2020-12-16 | 2021-03-19 | 兰州交通大学 | Preparation and application of metal atom doped hollow MXene quantum dot |
| CN115231682A (en) * | 2022-06-23 | 2022-10-25 | 天津市创嘉生物技术有限公司 | Aquaculture water purifying agent and preparation method thereof |
| CN116328802A (en) * | 2021-12-10 | 2023-06-27 | 华北电力大学（保定） | Preparation method of beta-FeOOH@MXene nanocomposite catalyst |
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