CN110102248A - A kind of surface oxygen defect porous metal oxide material and its preparation and application - Google Patents
A kind of surface oxygen defect porous metal oxide material and its preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of surface oxygen defect porous metal oxide material and its preparations and application.The preparation method of the surface oxygen defect porous metal oxide material forms clear solution the following steps are included: 1) by dissolving metal salts in organic solvent；2) clear solution in step 1) is mixed with mantle plate agent, obtains the dispersion liquid of the two full and uniform dispersion, is thoroughly mixed to form metal salt gel；3) metal salt gel obtained in step 2) is prepared into xerogel；4) by xerogel high-temperature calcination obtained in step 3), gained ash content is surface oxygen defect porous metal oxide；This method can synchronized compound go out surface oxygen defect porous metal oxide material.Preparation method is relatively easy, and the oxygen vacancies concentration of material surface is increased while forming porous structure, changes the electronic structure of material, can be applied to absorption, photoelectrocatalysis and field of batteries.
Description
Technical field
The present invention relates to field of material technology, espespecially a kind of surface oxygen defect porous metal oxide material and its preparation and
Using.
Background technique
Metal oxide or combined metal oxide semiconductor are widely used in photoelectrocatalysis, catalysis and solid state battery neck
Domain.The fixed many reactions of such as carbon dioxide reduction and nitrogen are often limited to the activation of specific small molecule, and solid material lacks
Fall into high activity site of the unsaturated coordination site introduced as molecular chemisorption and activation.As a result, reasonable defect work
Cheng Chengwei regulates and controls the passage means of surface reaction.Defect serves not only as the reaction site of molecular chemisorption, and for energy and
The transfer of electronics provides part path.Wherein, the vacancy defect as caused by the loss of atom in lattice structure or ion can have
Effect ground changes distribution of charges and electron energy level near point defect.Vacancy defect can also change the optics and light emitting of crystal
Matter can introduce different Physical and chemical characteristics.However, Lacking oxygen is the most common yin in metal oxide semiconductor
Ionic vacancies defect plays a crucial role in the various physics and chemical property for determining material, such as d0Ferromagnetism, resistance are opened
It closes, superconduction, phase transformation, photocatalytic effect, photoelectrochemical behaviour, piezoelectric response, redox active etc..In addition, Lacking oxygen is being made
To have minimum formation energy in the various defects of electron donor.Accordingly, it is considered in nanoscale domain oxide semiconductor uniqueness
The research of function, the formation to Lacking oxygen in metal oxide nanostructure, migration and identification is very important.Research hair
Existing, the Lacking oxygen of metal oxide surface can enhance absorption and activity function of the interface to molecule.
The regulation method of oxide surface Lacking oxygen mainly has doping method, different wet chemistrys and solid state chemistry at present
Method, anaerobic environment calcination method, hydrogen calcination method, electron radiation method and plasma asistance technology law etc..Wherein doping method includes: gold
Belong to ion doping, nonmetallic and nonmetal doping and codope；Wet chemistry and solid state chemistry method include: different humidifyings
It learns and solid state reduction method and different wet chemical oxidation methods；Plasma asistance technology law includes argon ion bombardment method, atom
Layer sedimentation and other plasma-assisted processes methods.The above method has complicated for operation, expensive, some shortage selection control
Property.However, the active site quantity and mass transfer reacted from surface consider, Recent study person's increasingly preference porous material,
These materials are because its own structure has a large amount of macropore, mesoporous and micropore, so that its specific surface area is larger, provide a large amount of
Reaction site, and pore structure is conducive to reaction molecular from liquid phase to the mass transport process of surface phase.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of surface oxygen defect porous metal oxide material and its
Preparation and application, the oxygen vacancies concentration of material surface can be increased while forming porous structure, changes the electricity of material
Minor structure can be applied to absorption, photoelectrocatalysis and field of batteries.
In order to reach the object of the invention, the present invention provides a kind of preparation sides of surface oxygen defect porous metal oxide
Method, including the following steps:
1) by dissolving metal salts in organic solvent, clear solution is formed；
2) clear solution in step 1) is mixed with mantle plate agent, obtains the dispersion liquid of the two full and uniform dispersion, fills
Divide and is mixed to form metal salt gel；
3) metal salt gel obtained in step 2) is prepared into xerogel；
4) by xerogel high-temperature calcination obtained in step 3), gained ash content is the oxidation of surface oxygen defect porous metals
Object；
Optionally, the preparation method of the surface oxygen defect porous metal oxide is made of above-mentioned steps.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, the metal be lanthanum, zirconium,
Iron, manganese, titanium, cobalt and nickel it is one or more；The metal salt is the nitrate or carbonate of above-mentioned metal.
Optionally, the metal is lanthanum and zirconium, and the molar ratio of the two is 1:10-10:1；
It is organic molten described in step 1) in the preparation method of oxygen defect porous metal oxide in surface provided by the invention
Agent is selected from one of ethyl alcohol, methanol, normal propyl alcohol and isopropanol or a variety of；The molar concentration of the metal salt organic solvent is 1-
100mMol/L, preferably molar concentration are 1mMol/L.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, the mMol be mM,
That is milliMol；
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, temperature is dissolved described in step 1)
Degree is 40-80 DEG C.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, metal salt described in step 2)
Mass ratio with soft template is 0.1-2:1, and preferably the mass ratio of metal salt and soft template is 0.2-2:1；
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, mantle plate described in step 2)
Agent is selected from one or both of organic polymer template or organic surface active agent.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, the organic surface active agent
Selected from triblock copolymer P123, propylene glycol block polyether L64, block copolymer P84, triblock copolymer F127 and poly- second two
One of alcohol PEG or a variety of；
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, the organic polymer template
Agent is selected from one of polystyrene PS, polymetylmethacrylate, poly 4 vinyl pyridine P4VP and PVAC polyvinylalcohol
Or it is a variety of.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, the organic polymer template
The partial size of agent is 100-400nm.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, xerogel described in step 3)
To be made by freeze-day with constant temperature, the drying temperature is 40-80 DEG C, and the drying time is 24-48h.
In the preparation method of oxygen defect porous metal oxide in surface provided by the invention, high temperature described in step 4) is forged
Burning temperature is 300-600 DEG C, calcination time 4-6h.
On the other hand, the present invention provides oxygen defect porous metal oxides in surface made from above-mentioned preparation method.
In oxygen defect porous metal oxide in surface provided by the invention, the surface oxygen defect porous metal oxide
Specific surface area be 60-120m2/g；Pore volume is 0.2-0.3ml/g；Average particle size is 1-30 μm.
On the other hand, the present invention provides above-mentioned surface oxygen defect porous metal oxides in absorption phosphate radical and/or arsenic
Application in acid group.
The preparation of metal oxide materials involved in the present invention is simple, increases material table while forming porous structure
The oxygen vacancies concentration in face.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by specification, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical solution of the present invention, and constitutes part of specification, with this
The embodiment of application technical solution for explaining the present invention together, does not constitute the limitation to technical solution of the present invention.
Fig. 1 is preparation method flow diagram of the present invention；
A is the preparation process schematic diagram of macropore LZO in Fig. 2, and b is macropore LZO electron microscope picture, and c is macropore LZO transmission
Electron microscope picture and distribution diagram of element, d are macropore LZO nitrogen adsorption desorption curve and pore size distribution figure.
Fig. 3 is the electron spin resonance map of macropore LZO and mesoporous LZO.
A is the preparation process schematic diagram of mesoporous LZO in Fig. 4, and b is mesoporous LZO transmission electron microscope figure；C is mesoporous LZO
Distribution diagram of element, d are mesoporous LZO nitrogen adsorption desorption curve and pore size distribution figure.
Fig. 5 is control (blank) LZO, the Phosphateadsorption dynamic experiment of macropore LZO and mesoporous LZO.
Fig. 6 is control LZO (blank), the Arsenate adsorption dynamic experiment of macropore LZO and mesoporous LZO.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to the present invention
Embodiment be described in detail.It should be noted that in the absence of conflict, in the embodiment and embodiment in the application
Feature can mutual any combination.
A kind of preparation method of surface oxygen defect porous metal oxide, including following step are provided in the embodiment of the present invention
It is rapid:
1) by dissolving metal salts in organic solvent, clear solution is formed；
2) clear solution in step 1) is mixed with mantle plate agent, obtains the dispersion liquid of the two full and uniform dispersion, fills
Divide and is mixed to form metal salt gel；
3) metal salt gel obtained in step 2) is prepared into xerogel；
4) by xerogel high-temperature calcination obtained in step 3), gained ash content is the oxidation of surface oxygen defect porous metals
Object；
Optionally, the preparation method of the surface oxygen defect porous metal oxide is made of above-mentioned steps.
In embodiments of the present invention, the metal is the one or more of lanthanum, zirconium, iron, manganese, titanium, cobalt and nickel；The metal
Salt is the nitrate or carbonate of above-mentioned metal.
Optionally, the metal is lanthanum and zirconium, and the molar ratio of the two is 1:10-10:1；
In embodiments of the present invention, organic solvent described in step 1) is in ethyl alcohol, methanol, normal propyl alcohol and isopropanol
It is one or more；The molar concentration of the metal salt organic solvent is 1-100mMol/L, and preferably molar concentration is 1mMol/L.
In embodiments of the present invention, solution temperature described in step 1) is 40-80 DEG C.
In embodiments of the present invention, the mass ratio of metal salt described in step 2) and soft template is 0.1-2:1, preferably golden
The mass ratio for belonging to salt and soft template is 0.2-2:1；
In embodiments of the present invention, the agent of mantle plate described in step 2) is selected from organic polymer template or organic surface is living
One or both of property agent.
In embodiments of the present invention, it is poly- to be selected from triblock copolymer P123, propylene glycol block for the organic surface active agent
One of ether L64, block copolymer P84, triblock copolymer F127 and polyethylene glycol PEG or a variety of；
In embodiments of the present invention, the organic polymer template is selected from polystyrene PS, polymethyl methacrylate
One of PMMA, poly 4 vinyl pyridine P4VP and PVAC polyvinylalcohol are a variety of.
In embodiments of the present invention, the partial size of the organic polymer template is 100-400nm.
In embodiments of the present invention, xerogel described in step 3) is to be made by freeze-day with constant temperature, and the drying temperature is
40-80 DEG C, the drying time is 24-48h.
In embodiments of the present invention, high-temperature calcination temperature described in step 4) is 300-600 DEG C, calcination time 4-6h.
According in oxygen defect porous metal oxide in surface made from above-mentioned preparation method, the porous gold of surface oxygen defect
The specific surface area for belonging to oxide is 60-120m2/g；Pore volume is 0.2-0.3ml/g；Average particle size is 1-30 μm.
Embodiment 1
Using lanthanum nitrate hexahydrate and five water zirconium nitrates as raw material, the molar ratio 1:1 of the two；
With average grain diameter for 200nm polystyrene sphere (PS) for soft template, soft template and lanthanum nitrate hexahydrate, five
The mass ratio of the sum of water zirconium nitrate is 10:1；
The preparation method is as follows:
Firstly, lanthanum nitrate hexahydrate and five water zirconium nitrates are dissolved in 60 DEG C of ethanol solutions (99vol.%) so that six water nitre
The molar concentration of sour lanthanum is 10mM, forms clear solution；
Secondly, clear solution and soft template are sufficiently mixed uniformly, metal salt gel is formed；
Later, obtained metal salt gel is put into 60 DEG C of heated at constant temperature casees, it is dry to form xerogel for 24 hours, it is to be cooled
After take out；
Finally, xerogel is placed in tube furnace, 4h, gained ash content are calcined at 500 DEG C under conditions of blowing air
As increase the La of Surface Oxygen hole concentration simultaneously with honeycomb structure2O3-ZrO2Composite metal oxide material (macropore
LZO), as shown in Figure 2.
Electron spin resonance atlas analysis shows (Fig. 3) that macropore LZO shows that oxygen vacancy concentration is obvious relative to blank LZO
Increase, while being speculated according to the covalency of La/Zr and oxygen, this Lacking oxygen belongs to the position Surface L a.
Embodiment 2
Using lanthanum nitrate hexahydrate and five water zirconium nitrates as raw material, the molar ratio of the two is 1:1；
With P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer) for soft template, soft template and six
The mass ratio of the sum of water lanthanum nitrate and five water zirconium nitrates is 1:1；
The preparation method is as follows:
Firstly, lanthanum nitrate hexahydrate and five water zirconium nitrates are dissolved in 60 DEG C of ethanol solutions (99vol.%) so that six water nitre
The mass concentration of sour lanthanum is 10mM, forms clear solution；
Secondly, clear solution and soft template P123 are sufficiently mixed uniformly, metal salt gel is formed；
Later, obtained metal salt gel is put into 60 DEG C of heated at constant temperature casees, it is dry to form xerogel for 24 hours, it is to be cooled
After take out；
Finally, xerogel is placed in tube furnace, 4h is calcined at 500 DEG C under conditions of blowing air, is had
20nm meso-hole structure increases the La of Surface Oxygen hole concentration simultaneously2O3-ZrO2Composite metal oxide material (mesoporous LZO), such as
Shown in Fig. 4.Electron spin resonance atlas analysis shows (Fig. 3) that mesoporous LZO shows that oxygen vacancy concentration is obvious relative to blank LZO
Increase, while being speculated according to the covalency of La/Zr and oxygen, this Lacking oxygen also belongs to the position Surface L a.
Comparative example 1
Using lanthanum nitrate hexahydrate and five water zirconium nitrates as raw material, the molar ratio of the two is 1:1；
It is not added with soft template, other preparation methods are identical as embodiment.
The preparation method is as follows:
Firstly, lanthanum nitrate hexahydrate and five water zirconium nitrates are dissolved in 60 DEG C of ethanol solutions (99vol.%) so that six water nitre
The mass concentration of sour lanthanum is 10mM, forms clear solution；
Later, obtained metal salt solution is put into 60 DEG C of heated at constant temperature casees, drying for 24 hours, forms powder, after cooling
It takes out；
Finally, powder is placed in tube furnace, 4h is calcined at 500 DEG C under conditions of blowing air, obtains blank
LZO。
Application examples 1:
At 25 DEG C, under the conditions of pH7.0, for PO4 3-The laboratory water distribution of (10mg/L, in terms of P), using consolidating for 0.2g/L
Liquid dosage adds material made from embodiment 1,2 and comparative example, carries out adsorption test.The result shows that material made from embodiment
Material is bigger to the adsorbance of phosphorus, and the rate of adsorption is fast.Its result is as shown in figure 5, the material eliminating rate of absorption of Examples 1 and 2 is opposite
~10% and~25% has been respectively increased in comparative example material.
Application examples 2:
At 25 DEG C, under the conditions of pH7.0, for AsO4 3-The laboratory water distribution of (10mg/L, in terms of As), using 0.2g/L's
Solid-liquid dosage adds material made from embodiment 1,2 and comparative example, carries out adsorption test.The result shows that made from embodiment
Material is bigger to the adsorbance of phosphorus, and the rate of adsorption is fast.Its result as shown in fig. 6, Examples 1 and 2 material eliminating rate of absorption phase
~25% and~30% have been respectively increased for comparative example material.
In conclusion this method can synchronized compound go out surface oxygen defect porous metal oxide material.Preparation method phase
To simple, the oxygen vacancies concentration of material surface is increased while forming porous structure, changes the electronic structure of material, it can
Applied to absorption, photoelectrocatalysis and field of batteries.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of surface oxygen defect porous metal oxide, including the following steps:
1) by dissolving metal salts in organic solvent, clear solution is formed；
2) clear solution in step 1) is mixed with mantle plate agent, obtains the dispersion liquid of the two full and uniform dispersion, it is sufficiently mixed
Conjunction forms metal salt gel；
3) metal salt gel obtained in step 2) is prepared into xerogel；
4) by xerogel high-temperature calcination obtained in step 3), gained ash content is surface oxygen defect porous metal oxide；
Metal in the metal oxide or the metal salt is the one or more of lanthanum, zirconium, iron, manganese, titanium, cobalt and nickel；Institute
State the nitrate or carbonate that metal salt is above-mentioned metal.
2. the preparation method of oxygen defect porous metal oxide in surface according to claim 1, wherein described in step 1)
Organic solvent is selected from one of ethyl alcohol, methanol, normal propyl alcohol and isopropanol or a variety of；The metal salt organic solvent it is mole dense
Degree is 1-100mMol/L, and preferably molar concentration is 1mMol/L.
3. the preparation method of oxygen defect porous metal oxide in surface according to claim 1, wherein described in step 1)
Solution temperature is 40-80 DEG C.
4. the preparation method of oxygen defect porous metal oxide in surface according to any one of claim 1 to 3, wherein
The mass ratio of metal salt described in step 2) and soft template is 0.1-2:1；
The agent of mantle plate described in step 2) is selected from one or both of organic polymer template or organic surface active agent.
5. the preparation method of oxygen defect porous metal oxide in surface according to claim 4, wherein organic surface
Activating agent be selected from triblock copolymer P123, propylene glycol block polyether L64, block copolymer P84, triblock copolymer F127 and
One of polyethylene glycol is a variety of；
The organic polymer template is selected from polystyrene, polymethyl methacrylate, poly 4 vinyl pyridine and polyethylene
One of alcohol is a variety of；
Optionally the partial size of the template is 100-400nm.
6. the preparation method of oxygen defect porous metal oxide in surface according to any one of claim 1 to 3, wherein
Xerogel described in step 3) is to be made by freeze-day with constant temperature, and the drying temperature is 40-80 DEG C, and the drying time is 24-
48h。
7. the preparation method of oxygen defect porous metal oxide in surface according to any one of claim 1 to 3, wherein
High-temperature calcination temperature described in step 4) is 300-600 DEG C, calcination time 4-6h.
8. oxygen defect porous metal oxide in surface made from preparation method described in a kind of any one of claims 1 to 7.
9. oxygen defect porous metal oxide in surface according to claim 8, wherein the surface oxygen defect porous metals
The specific surface area of oxide is 60-120m2/g；Pore volume is 0.2-0.3ml/g；Average particle size is 1-30 μm.
10. oxygen defect porous metal oxide in surface described in a kind of claim 8 or 9 is in absorption phosphate radical and/or arsenate
In application.
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| CN113603111A (en) * | 2021-08-23 | 2021-11-05 | 中国科学院宁波材料技术与工程研究所 | 4A zeolite with adjustable oxygen vacancy content and preparation method and application thereof |
| CN113801563A (en) * | 2021-09-16 | 2021-12-17 | 长沙民德消防工程涂料有限公司 | Photo-curing glass heat-insulating coating and preparation process thereof |
| CN114177901A (en) * | 2020-09-14 | 2022-03-15 | 四川大学 | Preparation method of mesoporous metal oxide catalytic material |
| CN114939407A (en) * | 2022-07-06 | 2022-08-26 | 四川大学 | Method for synthesizing loose porous manganese oxide and composite oxide thereof |
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