CN107986324A - A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure - Google Patents

A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure Download PDF

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CN107986324A
CN107986324A CN201711163898.4A CN201711163898A CN107986324A CN 107986324 A CN107986324 A CN 107986324A CN 201711163898 A CN201711163898 A CN 201711163898A CN 107986324 A CN107986324 A CN 107986324A
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carbonized material
activated carbon
perovskite structure
calcium titanate
elements
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曹小利
任铁真
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

The invention discloses a kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure, carrier is selected from one kind in the carbonized material (Carbon) of different biomass carbon sources, and the general formula of perovskite structure oxide is ABO3, wherein A is calcium, and B is titanium.Preparation method：Weigh carbonized material: potassium hydroxide: potassium carbonate: B bit elements mass ratio is dissolved in water for 1: 1: 2: 0.02~0.1, stir evenly, infiltrate its sufficient standing, then being mixed makes B element uniform load on carbonized material, carbonized material is set to obtain preliminary chemical etching at the same time, obtained mixture is dried, remove moisture, roasting heat treatment chemical activation is carried out to obtained product under the conditions of inert gas shielding, obtained product is neutralized through hydrochloric acid, deionized water is cleaned until pH=7~8, the calcium titanate nanoparticles with perovskite structure of activated carbon supported high degree of dispersion are made after drying.

Description

A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure
Technical field
The invention belongs to field of inorganic nonmetallic material, and in particular to a kind of calcium titanate of activated carbon supported perovskite structure The preparation method of nano material.
Background technology
It with general formula is ABO that perovskite structure oxide, which is,3Unique crystal structures oxide, A is generally rare earth or alkali Earth elements, B are period 3 transition metal.Because it is with good photocatalysis, electrocatalysis characteristic, and electrical conductivity is high, valency Lattice are cheap, are widely used in dye-sensitized solar cells (DSSC), lithium ion battery, solid fuel cell, sensor and The numerous areas such as the oxygen electrode electrocatalyst materials of noble metal are substituted, become research hotspot in chemistry, physics and Material Field.
The preparation method of perovskite structure oxide mainly has coprecipitation, solid phase method, sol-gel process, Hydrothermal Synthesiss Method and microemulsion method etc..Wherein, though coprecipitation cost is low, easy to operate, its preparation process is more, particle is easily reunited, compares table Area is low；Solid phase method has the advantages that equipment and easy to operate, but since different solid particles mix uneven, the calcium prepared The particle of titanium ore type oxide is larger, specific surface area is smaller；Sol-gel process synthesis temperature is low, and product purity is high, specific surface area Greatly, good dispersion, but the method has the shortcomings that technique is difficult to control, process conditions are harsh, of high cost；The letter of hydrothermal synthesis method technique Singly, the shortcomings that overcoming particle hard aggregation, but reaction is incomplete, process is difficult to control, to equipment requirement height；It is prepared by microemulsion method Particle size it is small, be evenly distributed, but production cost is high, is unfavorable for large-scale production.
The content of the invention
The present invention provides a kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure, this method The shortcomings that overcoming any of the above preparation method.This method equipment and easy to operate, cost is low, the Ca-Ti ore type oxygen being prepared Compound has the advantages that particle diameter is small, particle height disperses, specific surface area is big.
Technical scheme is as follows：
A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure, it is characterised in that this method Comprising：
Step 1, carbonized material carrier：Potassium hydroxide：Potassium carbonate：B bit elements, which are mixed in a certain ratio, is dissolved in water, is placed in beaker In, 5~10h is stood, it is fully infiltrated, then room temperature persistently stirs 5~12h on magnetic stirrer, makes B metallic elements equal Even load on the activated carbon, while makes activated carbon reach initial chemical etching；
Step 2, by the mixture that step 1 obtains in 100 DEG C of dry 12h, uniformly, which is charcoal for obtained product grinding The mixture of material uniform load B element；
Step 3, under nitrogen protective condition, chemical activation roasting heat treatment, temperature are carried out to the powdered product obtained by step 2 Spend for 600~900 DEG C, keep 2h, then Temperature fall to room temperature；
Step 4, the product obtained to step 3 carries out washing and drying treatment, you can obtains having the more of high-specific surface area Level hole activated carbon from activated sludge, and the calcium titanate nanoparticles with perovskite structure containing high degree of dispersion on activated carbon frame.
In the above method, the carrier is the different biomass carbon source warps such as Chinese ash leaf, pine needle, bagasse and corncob Temperature is 500 DEG C, keeps the charing process of 2h, obtained carbonized material.
In the above method, the carbonized material carrier need to be pre-processed：First use the hydrochloric acid solution pickling of 1mol/L 10h, it is therefore an objective to reduce the amount of the miscellaneous element in carbonized material, then cleaned with deionized water, then 100 DEG C of drying, grinding obtains institute Need carbonized material.
In the above method, the perovskite structure oxide is ABO3, wherein A bits element is Ca, from pickling The Ca elements that biomass carbon material contains itself after technique, without the oxide or calcium salt of additional calcium, B bits element is Ti elements, From titanyl compound.
In the above method, the carbonized material carrier：Potassium hydroxide：Potassium carbonate：B bits element is 1: 1: 2 in mass ratio: 0.02~0.1 proportional arrangement.
In the above method, roasting heat treatment process effect one is to be had the further chemical activation of carbonized material The multi-stage porous activated carbon from activated sludge of high-specific surface area, effect two are to make the Ca elements that itself are largely distributed on carbonized material and bear early period B positions metallic element in load acts on forming perovskite structure oxide nano particle, the two is carried out at the same time, and what is obtained has calcium The calcium titanate nanoparticles particle diameter of perovskite like structure is small, and high uniformity distribution is obtained on activated carbon frame.
The present invention has the following advantages：
1st, the biomass carbon material carrier that uses of the present invention have it is environmental-friendly, derive from a wealth of sources, be of low cost, made after activation The multistage pore canal activated carbon obtained has the advantages that specific surface area is big, adsorption capacity is strong, is conducive to perovskite structure oxide nanometer A large amount of uniform loads of particle.
2nd, the biomass carbon material in the present invention has the characteristic containing a variety of a large amount of miscellaneous elements, as K, Ca, Mg, Fe, S, P, N etc., wherein mainly based on Ca, reduces the amount of miscellaneous element after the cleaning of 1mol/L hydrochloric acid, but Ca constituent contents are also more, this ABO in invention3The Ca that A bits element in perovskite structure oxide itself contains from biomass carbon material after acid cleaning process Element, without the oxide or calcium salt of additional calcium, has reached saving material, reduces cost, the purpose that technique simplifies.
3rd, the present invention roasts heat treating process using chemical activation, first fully soaks carbonized material and B element compounds Moisten and be stirred, B element compounds is sufficiently mixed with carbonized material and reach uniform load, then by mixture in tube furnace Middle short time roasting heat treatment, the titanium elements on Ca elements and load early period for making itself to be largely distributed on activated carbon act on being formed Perovskite structure oxide (CaTiO3) nano particle, the perovskite structure oxide nano particle diameter is small, and in active frame High uniformity distribution is obtained on frame.This method equipment is simple at the same time, easy to operate, and production efficiency is high, can be mass-produced.
Brief description of the drawings
Fig. 1 is the Chinese ash leaf carbonized material (FLC), pine needle carbonized material (PNC), sweet that 1~6 pre-treatment step of embodiment obtains The XRF spectrograms of bagasse carbonized material (BC), corncob carbonized material (CC).
Fig. 2 is the XRD spectra for mixing titanium white wax tree leaf system row activated carbon that embodiment 1 and embodiment 2 obtain.Wherein curve (A) XRD spectra for being Ti-2-FAC, curve (B) are the XRD spectra of Ti-7-FAC.
Fig. 3 is SEM, TEM, EDS and the HRTEM collection of illustrative plates for the product that embodiment 1 obtains.(A) is wherein schemed to mix titanium white wax tree The SEM figures of leaf activated carbon Ti-2-FAC, the TEM that (B) is Ti-2-FAC scheme, and the EDS that (C) is Ti-2-FAC schemes, and (D) is Ti-2- The HRTEM figures of FAC.
Fig. 4 is the XRD spectra for the product that embodiment 3~5 obtains.Wherein curve (A) is to mix titanium pine needle active charcoal Ti-4- The XRD spectra of PAC, curve (B) are the XRD spectra for mixing titanium corncob activated carbon Ti-3-CAC, and curve (C) is to mix titanium bagasse The XRD spectra of activated carbon Ti-10-BAC.
Embodiment
To make those skilled in the art more fully understand technical scheme, next made using the embodiment having It is described in further detail.
Embodiment 1：
Support pre-treatment step：By Chinese ash leaf carbon source after deionized water is cleaned, dry 12h is placed in 100 DEG C of baking ovens, The moisture in mixture is removed, obtained material is placed in kiln, under nitrogen protection, is warming up to the speed of 10 DEG C/min 500 DEG C, 2h is kept, is cooled to room temperature under nitrogen atmosphere, obtains carbonized material；Obtained carbonized material is ground into fine powdered, then Cleaned with the HCl and deionized water of 1mol/L, reduce the amount of miscellaneous element in carbonized material, dry 12h, obtains in 100 DEG C of baking oven To the Chinese ash leaf carbonized material (FLC) for still containing more Ca elements.The x-ray fluorescence light of the carbonized material of different biomass carbon sources Spectrogram (XRF) as shown in Figure 1, showing the carbonized materials of different biomass carbon sources in still contain many Ca elements, and a small amount of K With Fe elements.
By Chinese ash leaf carbonized material carrier, KOH, K2CO3And TiO2By FLC: KOH: K2CO3: Ti=1: 1: 2: 0.02 matter The mixing of amount ratio is dissolved in water, is placed in beaker, stands 10h, it is fully infiltrated, then room temperature persistently stirs on magnetic stirrer 12h is mixed, obtained mixture is placed in 100 DEG C of baking ovens dry 12h, and obtained product grinding is uniform；The solid powder is placed in In tube furnace, under nitrogen protection, 800 DEG C are warming up to the speed of 10 DEG C/min, keep 2h, room is cooled under nitrogen atmosphere Temperature, obtains activation products；Obtained activation products are first cleaned with the HCl of 1mol/L, neutralized, then are cleaned with deionized water to pH= 7~8, dry 12h, obtains the activated carbon supported CaTiO with perovskite structure of Chinese ash leaf in 100 DEG C of baking oven3Nanometer Material.
Curve in the X-ray diffraction spectrogram such as Fig. 2 of titanium Chinese ash leaf activated carbon (Ti-2-FAC) is mixed made from the embodiment (A) shown in, respectively in 2 θ=23.1 ° in spectrogram, 33.2 °, 41.0 ° 47.6 °, 59.2 °, 69.5 ° of CaTiOs corresponding with 79.2 °3 (110) of crystal form, (112), (202), (220), (204), (224) and (116) crystal face (JCPDS, No.82-0228).Show Chinese ash leaf activated carbon surface forms CaTiO3Crystal type nano particle.The scanning electricity of product Ti-2-FAC made from the embodiment Mirror figure (SEM) is such as shown in Fig. 3 (A), can be observed that activated carbon surface is porous and coarse, the transmission electron microscope of Ti-2-FAC Collection of illustrative plates (TEM) is such as shown in Fig. 3 (B), and color higher depth represents particle, and shallower area represents the presence in hole, can substantially observe activity There is particle diameter about 2~10nm, and the CaTiO with perovskite structure that high uniformity disperses in charcoal frame3Nano particle.It is right The transmission electron microscope energy spectrum diagram (EDS) answered such as shown in Fig. 3 (C), contains Ca, Ti, O element really on provable activated carbon frame.For Further prove the CaTiO of perovskite structure3Formation, high resolution transmission electron microscopy spectrum has been carried out to Ti-2-FAC (HRTEM) such as Fig. 3 (D), show that crystal interplanar crystal spacing is 0.191nm, 0.219nm and 0.230nm in collection of illustrative plates, correspond to CaTiO3(220) of crystal form, (202) and (103) crystal face.
The result shows that in ACs frames, the CaTiO with perovskite structure is formd by Ti doping3Crystal type nano Grain.
Embodiment 2：
Support pre-treatment step is the same as pre-treatment step in embodiment 1.
By Chinese ash leaf carbonized material carrier, KOH, K2CO3And TiO2By FLC: KOH: K2CO3: Ti=1: 1: 2: 0.07 matter The mixing of amount ratio is dissolved in water, is placed in beaker, stands 10h, it is fully infiltrated, then room temperature persistently stirs on magnetic stirrer 12h is mixed, obtained mixture is placed in 100 DEG C of baking ovens dry 12h, and obtained product grinding is uniform；The solid powder is placed in In tube furnace, under nitrogen protection, 800 DEG C are warming up to the speed of 10 DEG C/min, keep 2h, room is cooled under nitrogen atmosphere Temperature, obtains activation products；Obtained activation products are first cleaned with the HCl of 1mol/L, neutralized, then are cleaned with deionized water to pH= 7~8, dry 12h, obtains the activated carbon supported CaTiO with perovskite structure of Chinese ash leaf in 100 DEG C of baking oven3Nanometer Material.
Curve in the X-ray diffraction spectrogram such as Fig. 2 of titanium Chinese ash leaf activated carbon (Ti-7-FAC) is mixed made from the embodiment (B) shown in, only there is peak at 2 θ=33.2 ° in spectrogram, show to form on Chinese ash leaf activated carbon frame faint CaTiO3Crystal type nano particle.Should be the result shows that difference Ti contents influence CaTiO3The power of crystal form.
Embodiment 3：
Support pre-treatment step：Carbon source is changed to pine needle, obtains pine needle carbonized material (PNC), other in embodiment 1 the same as pre-processing Step.
By pine needle carbonized material carrier, KOH, K2CO3And TiO2By PNC: KOH: K2CO3: Ti=1: 1: 2: 0.04 mass ratio Example mixing is dissolved in water, is placed in beaker, stands 8h, it is fully infiltrated, and then room temperature persistently stirs 8h on magnetic stirrer, Obtained mixture is placed in 100 DEG C of baking ovens dry 12h, and obtained product grinding is uniform；The solid powder is placed in tube furnace In, under nitrogen protection, 600 DEG C are warming up to the speed of 10 DEG C/min, keep 2h, be cooled to room temperature, obtain under nitrogen atmosphere Activation products；Obtained activation products are first cleaned with the HCl of 1mol/L, neutralized, then are cleaned with deionized water to pH=7~8, The dry 12h in 100 DEG C of baking oven, obtains CaTiO of the pine needle active charcoal load with perovskite structure3Nano material.
Curve (A) institute in the X-ray diffraction spectrogram such as Fig. 4 of titanium pine needle active charcoal (Ti-4-PAC) is mixed made from the embodiment Show equally peak occur at θ=23.1 ° of 2 θ=2,33.2 °, 41.0 ° 47.6 °, 59.2 °, 69.5 ° and 79.2 ° in spectrogram, show The CaTiO with perovskite structure is formd on pine needle active charcoal frame3Crystal type nano particle.
Embodiment 4：
Support pre-treatment step：Carbon source is changed to corncob, obtains corncob carbonized material (CC), other are the same as pre- in embodiment 1 Processing step.
By corncob carbonized material carrier, KOH, K2CO3And TiO2By CC: KOH: K2CO3: Ti=1: 1: 2: 0.03 quality Ratio mixing is dissolved in water, is placed in beaker, stands 5h, it is fully infiltrated, then room temperature persistently stirs on magnetic stirrer 10h, obtained mixture are placed in 100 DEG C of baking ovens dry 12h, and obtained product grinding is uniform；The solid powder is placed in pipe In formula stove, under nitrogen protection, 700 DEG C are warming up to the speed of 10 DEG C/min, keep 2h, be cooled to room temperature under nitrogen atmosphere, Obtain activation products；Obtained activation products are first cleaned with the HCl of 1mol/L, neutralized, then with deionized water clean to pH=7~ 8, dry 12h, obtains the activated carbon supported CaTiO with perovskite structure of corncob in 100 DEG C of baking oven3Nano material.
Curve (B) in the X-ray diffraction spectrogram such as Fig. 4 of titanium corncob activated carbon (Ti-3-CAC) is mixed made from the embodiment It is shown, equally occur CaTiO in spectrogram3The correspondence peak of crystal form, shows to form CaTiO on corncob activated carbon frame3Crystal form is received Rice grain.
Embodiment 5：
Support pre-treatment step：Carbon source is changed to bagasse, obtains bagasse carbonized material (BC), other are the same as pre- in embodiment 1 Processing step.
By bagasse carbonized material carrier, KOH, K2CO3And TiO2By BC: KOH: K2CO3: Ti=1: 1: 2: 0.1 mass ratio Example mixing is dissolved in water, is placed in beaker, stands 5h, it is fully infiltrated, and then room temperature persistently stirs 5h on magnetic stirrer, Obtained mixture is placed in 100 DEG C of baking ovens dry 12h, and obtained product grinding is uniform；The solid powder is placed in tube furnace In, under nitrogen protection, 900 DEG C are warming up to the speed of 10 DEG C/min, keep 2h, be cooled to room temperature, obtain under nitrogen atmosphere Activation products；Obtained activation products are first cleaned with the HCl of 1mol/L, neutralized, then are cleaned with deionized water to pH=7~8, The dry 12h in 100 DEG C of baking oven, obtains CaTiO of the bagasse active carbon load with perovskite structure3Nano material.
Curve in the X-ray diffraction spectrogram such as Fig. 4 of titanium bagasse active carbon (Ti-10-BAC) is mixed made from the embodiment (C) shown in, show to form CaTiO on bagasse active carbon frame3Crystal type nano particle.

Claims (6)

  1. A kind of 1. preparation method of the calcium titanate nano material of activated carbon supported perovskite structure, it is characterised in that this method bag Contain：
    Step 1, carbonized material carrier: potassium hydroxide: potassium carbonate: B bit elements, which are mixed in a certain ratio, is dissolved in water, is placed in beaker, 5~10h is stood, it is fully infiltrated, then room temperature persistently stirs 5~12h on magnetic stirrer, makes B metallic elements uniform Load on the activated carbon, while makes activated carbon reach initial chemical etching；
    Step 2, the dry 12h of 100 DEG C of mixture step 1 obtained, obtained product grinding is uniform, and the product is equal for carbonized material The mixture of even load B element；
    Step 3, under nitrogen protective condition, chemical activation roasting heat treatment is carried out to the powdered product obtained by step 2, temperature is 600~900 DEG C, 2h is kept, then Temperature fall to room temperature；
    Step 4, the product obtained to step 3 carries out washing and drying treatment, you can obtains the multi-stage porous with high-specific surface area Activated carbon from activated sludge, and on activated carbon frame the perovskite structure containing high degree of dispersion calcium titanate nanoparticles.
  2. 2. the method as described in claim 1, it is characterised in that the carrier described in step 1 is Chinese ash leaf, pine needle, sugarcane The difference biomass carbon source such as slag and corncob, is 500 DEG C through temperature, keeps the charing process of 2h, obtained carbonized material.
  3. 3. the method as described in claim 1, it is characterised in that the carbonized material carrier described in step 1 need to be pre-processed：First Using the hydrochloric acid solution pickling 10h of 1mol/L, it is therefore an objective to the amount of the miscellaneous element in carbonized material is reduced, then is cleaned with deionized water, Then 100 DEG C of drying, grinding obtain required carbonized material.
  4. 4. the method as described in claim 1, it is characterised in that the general formula of the perovskite structure oxide is ABO3, wherein A bits element is Ca, the Ca elements that biomass carbon material contains itself after acid cleaning process, without additional calcium oxide or Calcium salt, B bits element is Ti elements, from titanyl compound.
  5. 5. the method as described in claim 1, it is characterised in that carbonized material carrier in step 1: potassium hydroxide: potassium carbonate: B Element is 1: 1: 2: 0.02~0.1 proportional arrangement in mass ratio.
  6. 6. the method as described in claim 1, it is characterised in that it is to make carbonized material that heat treatment process effect one is roasted in step 3 Further chemical activation obtains the multi-stage porous activated carbon from activated sludge with high-specific surface area, and effect two is to make itself on carbonized material big The Ti element interactions measured on the Ca elements and load early period of distribution form perovskite structure oxide (CaTiO3) nano particle, two Person is carried out at the same time, and obtains the CaTiO with perovskite structure3Nano particle diameter is small, and height is obtained on activated carbon frame It is uniformly distributed.
CN201711163898.4A 2017-11-17 2017-11-17 A kind of preparation method of the calcium titanate nano material of activated carbon supported perovskite structure Pending CN107986324A (en)

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CN109894132A (en) * 2018-08-28 2019-06-18 福建省农业科学院农业工程技术研究所 The method for preparing Carbou doped titanium-oxide visible light catalyst as carbon source using waste
CN110449164A (en) * 2019-09-19 2019-11-15 西安凯立新材料股份有限公司 The preparation method of perofskite type oxide modified activated carbon supported precious metal catalyst
CN112495348A (en) * 2020-11-11 2021-03-16 陕西浦士达环保科技有限公司 Activated carbon capable of removing trichloromethane
CN114014301A (en) * 2021-11-17 2022-02-08 北京师范大学 Synthetic method of fluorescent carbon nano onion
CN114100600A (en) * 2020-08-28 2022-03-01 中国科学院大连化学物理研究所 Perovskite material and preparation method and application thereof
CN114195228A (en) * 2021-12-14 2022-03-18 中南大学 Wastewater organic pollutant degradation system based on perovskite three-dimensional electrode

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