CN105289421B - Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol - Google Patents
Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol Download PDFInfo
- Publication number
- CN105289421B CN105289421B CN201510852300.7A CN201510852300A CN105289421B CN 105289421 B CN105289421 B CN 105289421B CN 201510852300 A CN201510852300 A CN 201510852300A CN 105289421 B CN105289421 B CN 105289421B
- Authority
- CN
- China
- Prior art keywords
- graphene
- coal base
- catalytic reduction
- macroscopic material
- photo catalytic
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a kind of graphene macroscopic material photo catalytic reduction CO2The equipment for preparing methanol, including reaction chamber, multiple uviol lamps are provided with the inwall of the reaction chamber, the reaction bulb for containing solution medium is provided with the reaction chamber, the bottom of the reaction bulb is provided with the heater for being heated to the solution medium, the top of the reaction bulb is connected with condenser pipe, and the condenser pipe is connected with condensate liquid collecting tank, and the bottom of the reaction bulb passes through CO2Pipeline and the CO outside reaction chamber2Gas cylinder is connected, and is provided with the reaction bulb on porous barrier, the porous barrier and is provided with catalyst filling, the CO2Flow control valve is provided with pipeline.Equipment progress graphene macroscopic material photo catalytic reduction CO is utilized present invention also offers a kind of2The method for preparing methanol.The present invention uses graphene macroscopic material for photochemical catalyst, excellent catalytic effect, high catalytic efficiency, and methanol yield is high.
Description
Technical field
The invention belongs to photocatalysis technology field, and in particular to a kind of graphene macroscopic material photo catalytic reduction CO2Prepare
The device and method of methanol.
Background technology
Graphene is sent out in succession as carbon material branch of family rising star, its more and more peculiar physicochemical properties
Now and in the performance out of the ordinary of numerous application fields, the hot fields of scientific research are rapidly become.Graphene is considered as institute
There is sp2The basic structural unit of hydridization carbonaceous material, it is to construct specific structure and the carbonaceous material of function brings new machine
Meet.Assembled by structure, graphene sheet layer can build the functionalization graphene macroscopic material with specific structure, by microcosmic stone
The excellent properties reflection of black alkene lamella is in macroscopic material, such as outstanding mechanical property, quick electron mobility, the ratio of super large
Surface area and good adsorption capacity etc., make functionalization graphene macroscopic material in catalysis, absorption, energy storage, ultracapacitor
And the field such as biological medicine shows good application prospect.
CO2As a kind of abundant potential carbon source, it is converted, the exploitation using technology and application are in the range of future world
Realize the important research direction of the strategy of sustainable development.Wherein, photo catalytic reduction CO2Chemical energy directly is converted light energy into, it is green
Color environment-protection low-consumption, is advantageously implemented recycling for carbon, and as CO2Convert and utilize most one of technology of prospect.However,
In existing photocatalytic reaction device, catalyst is more to be uniformly mixed in reaction medium with molecule, causes reaction product difficult
In separating from reaction system, and make catalyst service life shorten can not to be used repeatedly.Obviously, this is certain
Photo catalytic reduction CO is limited in degree2The industrialization promotion and application of technology.
Therefore, one kind is researched and developed using functionalization graphene macroscopic material photo catalytic reduction CO2Methanol technology is prepared, not only may be used
To widen the application approach of graphene macroscopic material, and catalyst can not be repeatedly during can solving light-catalyzed reaction
The problem of using, with good economic benefit.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of graphene macroscopic view for above-mentioned the deficiencies in the prior art
Material light catalysis reduces CO2The equipment for preparing methanol.Graphene macroscopic material photo catalytic reduction CO can be carried out using the equipment2
Prepare methanol, preparation process environmental protection, simple to operate, graphene macroscopic material shows excellent photocatalysis performance, methanol
High conversion rate.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of graphene macroscopic material photocatalysis is also
Former CO2The equipment for preparing methanol, it is characterised in that including reaction chamber, is provided with multiple uviol lamps on the inwall of the reaction chamber,
The reaction bulb for containing solution medium is provided with the reaction chamber, the bottom of the reaction bulb is provided with for described molten
The heater that liquid medium is heated, the top of the reaction bulb is connected with condenser pipe, the condenser pipe and condensate liquid collecting tank
Connection, the bottom of the reaction bulb passes through CO2Pipeline and the CO outside reaction chamber2Gas cylinder is connected, and is provided with the reaction bulb
Catalyst filling, the CO are provided with porous barrier, the porous barrier2Flow control valve is provided with pipeline.
Above-mentioned graphene macroscopic material photo catalytic reduction CO2The equipment for preparing methanol, it is characterised in that：The reaction chamber
To be closed at both ends columnar structured, the quantity of the uviol lamp is six, and six uviol lamp uniform ring cloth are in reaction chamber
Inwall on.
Above-mentioned graphene macroscopic material photo catalytic reduction CO2The equipment for preparing methanol, it is characterised in that：The reaction bulb
Material be quartz glass.
Above-mentioned graphene macroscopic material photo catalytic reduction CO2The equipment for preparing methanol, it is characterised in that：It is described it is porous every
Hole in plate is circular port, and the aperture of the circular port is 0.5mm~1mm.
In addition, utilizing the said equipment progress graphene macroscopic material photo catalytic reduction CO present invention also offers a kind of2System
The method of standby methanol, it is characterised in that this method comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3Mixing is molten
NaOH and Na in liquid2SO3Concentration be 0.05~0.15mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb as solution medium, will be walked
Graphene macroscopic material described in rapid one is added in reaction bulb as catalyst filling, then using heater by solution medium
Temperature be heated to 68 DEG C~72 DEG C, CO is utilized afterwards2Gas cylinder is passed through CO into reaction bulb2, and by flow control valve by CO2
Flow be adjusted to 50mL/min~150mL/min, finally open uviol lamp, ultraviolet light intensity of illumination be 300 μ W/cm2~
500μW/cm2Under conditions of carry out photo catalytic reduction CO2Processing, methanol is obtained in condensate liquid collecting tank.
Above-mentioned method, it is characterised in that use anthracite to prepare graphene macroscopic material for raw material described in step one
Detailed process be：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of fine Coal
The microfine coal, is then placed in graphite crucible by powder, temperature be 2400 DEG C~2600 DEG C under conditions of insulation 2.5h~
3.5h, obtains graphitized charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base oxidation
Graphene；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, using electronation self-assembly method prepare
Coal base graphene hydrogel；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be -55 DEG C~-15 DEG C under conditions of it is cold
Dry 36h~48h is freezed, aeroge is obtained；
Step 105, under inert atmosphere protection, by aeroge described in step 104 with 5 DEG C/min~10 DEG C/min liter
Warm speed is warming up to constant temperature 1h~4h after 550 DEG C~850 DEG C and made annealing treatment, and coal base graphene macroscopic view is obtained after natural cooling
Material.
Above-mentioned method, it is characterised in that coal base graphite oxide is prepared using improvement Hummers methods described in step 102
The detailed process of alkene is：By graphitized charcoal, sodium nitrate, potassium permanganate and mass concentration be 98% the concentrated sulfuric acid in mass ratio 1:
(0.5~1): 5: after (30~40) are well mixed, stir 10min~50min under conditions of temperature is 0 DEG C~20 DEG C, then
30 DEG C~40 DEG C stirring 100min~300min are warming up to, stirring 10min~20min after 90 DEG C~100 DEG C is warming up to afterwards, plus
Enter after deionized water is diluted, use the method for dropwise addition to add mass concentration for 30% hydrogen peroxide solution, after stirring
Pickling, washing, filtering and drying process are carried out successively, obtain coal base graphene oxide；The addition of the deionized water is stone
40~60 times of inkization carbonaceous amount, the addition of the hydrogen peroxide solution is equal with the quality of potassium permanganate.
Above-mentioned method, it is characterised in that coal base graphene is prepared using electronation self-assembly method described in step 103
The detailed process of hydrogel is：The coal base graphene oxide is added into ultrasonic disperse in deionized water and uniformly, obtains coal base oxygen
The coal base graphene oxide water solution, is then well mixed and obtains mixed liquor, afterwards by graphite aqueous solution with ethylenediamine
The mixed liquor is obtained into coal Ji Shimoxishui after 3h~8h, natural cooling is incubated under conditions of temperature is 90 DEG C~120 DEG C
Gel；The concentration of the coal base graphene oxide water solution is 2g/L~6g/L, in the mixed liquor coal base graphene oxide with
The mass ratio of ethylenediamine is (0.2~0.75): 1.
Above-mentioned method, it is characterised in that the addition of catalyst filling described in step 3 is：In every liter of solution medium
Add 0.5g~5g catalyst fillings.
The present invention has advantages below compared with prior art：
1st, using coal as raw material ultrapure fine graphitic charcoal is made through high-temperature process, and then prepare the oxidation of coal base in the present invention
Graphene, its raw material sources are extensive, with low cost, are conducive to large-scale production, it is possible to achieve the clean utilization of coal resources.
2nd, the photocatalytic reactor that the present invention is designed, its structure novel and unique is scientific and reasonable, uses easy to operate, energy
Efficiently separating for post catalyst reaction and reaction medium is enough realized, and reaches that the purpose of regeneration can be repeated several times in catalyst.
3rd, the photocatalytic reactor that the present invention is designed, ultraviolet source therein uses common uviol lamp, and its cost is low
Honest and clean, service life is long, can realize the influence for inquiring into light intensity to photocatalysis performance by adjusting uviol lamp number.
4th, the photocatalytic reactor that the present invention is designed, reaction bulb CO therein2Intake method is using bottom in and top out adverse current
Dividing plate in contact, reaction bulb is to CO2Gas plays equally distributed effect, so as to be conducive to CO2Gas and liquid medium and urge
Fully contacted between agent.
5th, the photocatalytic reactor that the present invention is designed finally is provided with heater and air inlet pipe, can not only carry out photocatalysis
Reduce CO2Experiment, can also meet photocatalytic degradation water pollutant experiment progress, probe into temperature, gas with various atmosphere
Or influence of the dissolved oxygen solubility to catalysis material photocatalysis performance.
6th, the present invention uses anthracite to prepare graphene macroscopic material for raw material, and it shows significantly in microstructure
Two-dimensional graphene lamellar structure, these flexible sheets are stacked, staggeredly in an assembling process, form the netted hole knot of prosperity
Structure, Size Distribution is in micron to sub-micrometer range.This special three-dimensional network hole is internally formed logical in graphene macroform
Smooth mass transfer channel, can provide the path of good microenvironment and rapid electric charge transfer for light-catalyzed reaction.
7th, the present invention uses anthracite to prepare graphene macroscopic material for raw material, and it has flourishing three-dimensional netted hole knot
Structure and multi-disc layer structure, in photo catalytic reduction CO2Substantial amounts of CO can be absorbed by preparing in the course of reaction of methanol2, improve
CO2Residence time of the gas in reaction system, be conducive to CO2Gas and catalyst and reaction medium are fully contacted；Secondly this
It is kind special it is mesh-structured unobstructed mass transfer channel is internally formed at it, provides good microenvironment and quickly for chemical reaction
The path of transfer charge；In addition, the oxygen-containing functional group not reduced thoroughly and avtive spot that graphene macroscopic material surface retains,
It is also beneficial to improve its photocatalysis performance.
8th, the present invention uses graphene macroscopic material for photochemical catalyst, excellent catalytic effect, high catalytic efficiency, methanol yield
It is high.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Brief description of the drawings
Fig. 1 is graphene macroscopic material photo catalytic reduction CO of the present invention2Prepare the structural representation of the equipment of methanol.
Fig. 2 is the partial enlarged drawing at A in Fig. 1.
Fig. 3 is distribution schematic diagram of the uviol lamp of the present invention on reaction chamber interior wall.
Fig. 4 is the SEM photograph of the graphene macroscopic material (RGO) of the embodiment of the present invention 2.
Fig. 5 is the XRD spectrum of the graphitized charcoal of the embodiment of the present invention 2 (TXC).
Fig. 6 is the XRD spectrum of the coal base graphene oxide (CGO) of the embodiment of the present invention 2 and graphene macroscopic material (RGO).
Fig. 7 is the coal base graphene oxide (CGO) of the embodiment of the present invention 2 and the infrared spectrum of graphene macroscopic material (RGO)
Figure.
Fig. 8 is the Raman spectrogram of the graphene macroscopic material (RGO) of the embodiment of the present invention 2.
Fig. 9 is the coal base graphene oxide (CGO) of the embodiment of the present invention 2 and graphene macroscopic material (RGO) photo catalytic reduction
CO2Obtained methanol yield versus time curve.
Description of reference numerals：
1-reaction chamber；2-solution medium；3-reaction bulb；
4-heater；5-catalyst filling；6-uviol lamp；
7-condenser pipe；8-condensate liquid collecting tank； 9—CO2Pipeline；
10-flow control valve； 11—CO2Gas cylinder；12-porous barrier.
Embodiment
Graphene macroscopic material photo catalytic reduction CO of the present invention2The equipment for preparing methanol is described by embodiment 1.
Embodiment 1
As shown in Figure 1-2, graphene macroscopic material photo catalytic reduction CO of the present invention2Preparing the equipment of methanol includes reaction chamber
1, it is provided with multiple uviol lamps 6, the reaction chamber 1 on the inwall of the reaction chamber 1 and is provided with for containing solution medium 2
Reaction bulb 3, the bottom of the reaction bulb 3 is provided with the heater 4 for being heated to the solution medium 2, the reaction
The top of bottle 3 is connected with condenser pipe 7, and the condenser pipe 7 is connected with condensate liquid collecting tank 8, and the bottom of the reaction bulb 3 passes through
CO2The pipeline 9 and CO outside reaction chamber 12Gas cylinder 11 is connected, and porous barrier 12 is provided with the reaction bulb 3, described porous
Catalyst filling 5, the CO are provided with dividing plate 122Flow control valve 10 is provided with pipeline 9.
As shown in figure 3, the reaction chamber 1 is closed at both ends columnar structured, the quantity of the uviol lamp 6 is six,
Six uniform ring cloth of uviol lamp 6 are on the inwall of reaction chamber 1.
In the present embodiment, the material of the reaction bulb 3 is quartz glass.
In the present embodiment, the hole in the porous barrier 12 is circular port, and the aperture of the circular port is 0.5mm~1mm.
The present invention carries out graphene macroscopic material photo catalytic reduction CO using equipment as described in Example 12Prepare methanol
Method is described by embodiment 2-5.
Embodiment 2
With reference to Fig. 1 to 3, the present embodiment carries out graphene macroscopic material photo catalytic reduction using equipment as described in Example 1
CO2The method for preparing methanol comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material, detailed process is：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of fine Coal
The microfine coal, is then placed in graphite crucible by powder, is incubated 3h under conditions of temperature is 2500 DEG C, obtains graphitization
Charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base oxidation
Graphene, detailed process is：By the concentrated sulfuric acid in mass ratio 1 that graphitized charcoal, sodium nitrate, potassium permanganate and mass concentration are 98%
: after 0.75: 5: 35 is well mixed, 30min is stirred under conditions of temperature is 10 DEG C, 35 DEG C of stirring 120min are then heated to,
Be warming up to afterwards after 95 DEG C and stir 15min, add after deionized water is diluted, use dropwise addition method add mass concentration for
30% hydrogen peroxide solution, carries out pickling, washing, filtering and drying process, obtains coal base graphite oxide successively after stirring
Alkene；The addition of the deionized water is 50 times of graphitized charcoal quality, the addition and potassium permanganate of the hydrogen peroxide solution
Quality it is equal；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, using electronation self-assembly method prepare
Coal base graphene hydrogel, detailed process is：The coal base graphene oxide is added into ultrasonic disperse in deionized water uniformly, to obtain
To coal base graphene oxide water solution, then the coal base graphene oxide water solution is well mixed with ethylenediamine and mixed
The mixed liquor, is incubated after 5h, natural cooling obtains coal base graphene water-setting afterwards by liquid under conditions of temperature is 100 DEG C
Glue；The concentration of the coal base graphene oxide water solution is coal base graphene oxide and ethylenediamine in 4g/L, the mixed liquor
Mass ratio is 0.5: 1；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be -20 DEG C under conditions of be freeze-dried
40h, obtains aeroge；
Step 105, under inert atmosphere protection, aeroge described in step 104 is heated up with 8 DEG C/min heating rate
Constant temperature 3h is made annealing treatment after to 600 DEG C, and coal base graphene macroscopic material is obtained after natural cooling；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3Mixing is molten
NaOH and Na in liquid2SO3Concentration be 0.1mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb 3 as solution medium 2, will
Graphene macroscopic material described in step one is added in reaction bulb 3 as catalyst filling 5, the addition of the catalyst filling 5
Measure and be：1g catalyst fillings 5 are added in every liter of solution medium 2, then the temperature of solution medium 2 are heated to using heater 4
70 DEG C, CO is utilized afterwards2Gas cylinder 11 is passed through CO into reaction bulb 32, and by flow control valve 10 by CO2Flow be adjusted to
100mL/min, finally opens uviol lamp 6, is 400 μ W/cm in the intensity of illumination of ultraviolet light2Under conditions of carry out photo catalytic reduction
CO2Processing, methanol is obtained in condensate liquid collecting tank 8.
Fig. 4 is the SEM photograph of graphene macroscopic material (RGO) manufactured in the present embodiment.As shown in Figure 4, using this implementation
The graphene macroscopic material (RGO) that example is prepared shows obvious two-dimensional graphene lamellar structure in microstructure, these
Flexible sheet is stacked, staggeredly in an assembling process, forms the netted pore structure of prosperity, Size Distribution is in micron to sub-micron
Scope.This special three-dimensional network hole is internally formed unobstructed mass transfer channel in graphene macroform, can be anti-for chemistry
The path of good microenvironment and rapid electric charge transfer should be provided.
Fig. 5 is the XRD spectrum of graphitized charcoal manufactured in the present embodiment (TXC).As shown in Figure 5, obtained through high-temperature process
There is very sharp characteristic diffraction peak near 2 θ=26.5 ° in graphitized charcoal (TXC), forms obviously crystal knot
Structure, fragrant ring carbon stratum reticulare piece is larger, and synusia piles up height, and the XRD spectrum with high purity graphite is basically identical, illustrates the stone of graphitized charcoal
Blackization degree is very high.
Fig. 6 is the XRD spectrum of graphene macroscopic material (RGO) manufactured in the present embodiment and coal base graphene oxide (CGO).
It will be appreciated from fig. 6 that graphitized charcoal is aoxidized after coal-forming base graphene oxide (CGO) by strong oxidizer, graphitized charcoal at 2 θ=26.5 °
Characteristic peak disappears substantially, and occurs new characteristic diffraction peak at 2 θ=11 °, shows have substantial amounts of oxygen-containing functional group to introduce TXC
Interlayer.And the graphene macroscopic material synthesized using coal base graphene oxide through chemical reduction method, without obvious sharp diffraction
Peak, the diffraction maximum that there is peak type wideization only near 2 θ=26 °, shows that coal base graphene oxide in reduction process, contains
Oxygen functional group gradually comes off, and original interlayer orderly accumulation is destructurized, obtains by individual layer or few layer graphene synusia heap
Product, the graphene macroscopic material folded.
Fig. 7 is the infrared spectrum of graphene macroscopic material (RGO) manufactured in the present embodiment and coal base graphene oxide (CGO)
Figure.It can be seen from figure 7 that coal base graphene oxide (CGO) is in 1630cm-1Place occurs in that graphene crystal sp2C in structure
=C stretching vibration peak, in 1740cm-1The absworption peak at place is the stretching vibration peak of C=O on graphene oxide carboxyl, and
870cm-1The absworption peak that place occurs is the vibration absorption peak of epoxy radicals, as known from the above, and obtained coal base is aoxidized through strong oxidizer
Surface of graphene oxide contains the functional groups such as abundant carboxyl, hydroxyl, and the presence of these oxygen-containing functional groups can cause coal base oxygen
Graphite alkene has good hydrophily.The graphene macroscopic material sample obtained by electronation, its infrared absorption peak with
Coal base graphene oxide is compared, and the absworption peak of oxygen-containing functional group weakens to a certain extent, shows to slough after electronation
Part oxygen-containing functional group, in addition, in 1562cm-1The absworption peak that place occurs is attributed to the skeletal vibration peak of graphene sheet layer.
Raman spectrum is the powerful measure for studying graphene-based material, can be used to distinguish orderly and unordered carbon crystal knot
Structure.In the Raman spectrogram of carbon material, in 1350cm-1And 1580cm-1There are two important characteristic peaks at position, be referred to as D peaks
With G peaks.Wherein D peaks are due to that unordered or fault of construction inside carbon material induces, illustrate material internal the degree of disorder and
Defect level；G peaks then mainly reflect the degree of graphitization of carbon material.ID/IGThe relative intensity between D peaks and G peaks is represented, it
The unordered degree and defect closeness of sample can be reflected, its ratio is bigger, illustrates that the order of carbon material crystalline structure is got over
Difference, defect is more.Carbon material is in 2700cm-1Nearby also there is 2D peak, it comes from double resonance between the paddy of Raman scattering, typically
For judging the difference between body phase graphite and few layer graphite (or graphene).IG/I2DFew layer of graphite carbon materials are qualitatively reacted
The number situation of single-layer graphene, I in materialG/I2DRatio it is smaller, show that the number of plies of graphene is fewer.Can from Fig. 8
Go out, there is D peaks and G peaks, and I simultaneously in graphene macroscopic materialD/IGValue about 1.00, illustrates the macroscopical material of graphene prepared
The internal degree of disorder of material is high, and defect level is big.In addition, positioned at 2700cm-1Vicinity, RGO also occurs in that weaker and wideization
2D peaks, its IG/I2DValue is larger, shows that the RGO of the preparation number of plies is more.
Respectively with graphene macroscopic material (RGO) and coal base graphene oxide (CGO) for photocatalysis under ultraviolet light conditions
Agent, investigates both to CO respectively2The catalytic activity of photo catalytic reduction process, obtains light-catalyzed reaction knot under different photochemical catalysts
Really, as shown in Figure 9.It can be seen in figure 9 that under same catalyst, methanol yield is in increase trend with the extension in reaction time,
Because CO2Absorption be a Dynamic Accumulation process, the yield of methanol is also a Dynamic Accumulation process.With lamella CGO
For catalyst photo catalytic reduction CO2, the yield of methanol is only up to 5.34 μm of ol/gcat.And using graphene macroform RGO as
Catalyst photo catalytic reduction CO2When, the yield of methanol reaches as high as 65.91 μm of ol/gcat under similarity condition.This is due to
Obtained RGO has in the three-dimensional netted pore structure and multi-disc layer structure of prosperity, course of reaction can absorb big inside RGO
The CO of amount2, improve CO2Residence time of the gas in reaction system, be conducive to CO2Gas and catalyst and reaction medium
Fully contact；Secondly it is this it is special it is mesh-structured unobstructed mass transfer channel is internally formed at it, is provided well for chemical reaction
Microenvironment and fast transfer electric charge path；In addition, the oxygen-containing functional group not reduced thoroughly and activity that RGO surfaces retain
Site, is also beneficial to improve its photocatalysis performance.
Embodiment 3
With reference to Fig. 1 to 3, the present embodiment carries out graphene macroscopic material photo catalytic reduction using equipment as described in Example 1
CO2The method for preparing methanol comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material, detailed process is：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of fine Coal
The microfine coal, is then placed in graphite crucible by powder, is incubated 3.5h under conditions of temperature is 2500 DEG C, obtains graphitization
Charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base oxidation
Graphene, detailed process is：By the concentrated sulfuric acid in mass ratio 1 that graphitized charcoal, sodium nitrate, potassium permanganate and mass concentration are 98%
: after 0.5: 5: 30 is well mixed, 10minmin is stirred under conditions of temperature is 20 DEG C, 30 DEG C of stirrings are then heated to
150min, is warming up to after 90 DEG C and stirs 20min afterwards, after addition deionized water is diluted, and matter is added using the method for dropwise addition
The hydrogen peroxide solution that concentration is 30% is measured, pickling, washing, filtering and drying process is carried out after stirring successively, obtains coal base
Graphene oxide；The addition of the deionized water is 40 times of graphitized charcoal quality, the addition of the hydrogen peroxide solution with
The quality of potassium permanganate is equal；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, using electronation self-assembly method prepare
Coal base graphene hydrogel, detailed process is：The coal base graphene oxide is added into ultrasonic disperse in deionized water uniformly, to obtain
To coal base graphene oxide water solution, then the coal base graphene oxide water solution is well mixed with ethylenediamine and mixed
The mixed liquor, is incubated after 8h, natural cooling obtains coal base graphene hydrogel afterwards by liquid under conditions of temperature is 90 DEG C；
The concentration of the coal base graphene oxide water solution is the quality of coal base graphene oxide and ethylenediamine in 6g/L, the mixed liquor
Than for 0.2: 1；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be -15 DEG C under conditions of be freeze-dried
36h, obtains aeroge；
Step 105, under inert atmosphere protection, by aeroge described in step 104 with 10 DEG C/min heating rate liter
Temperature is made annealing treatment to constant temperature 4h after 550 DEG C, and coal base graphene macroscopic material is obtained after natural cooling；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3Mixing is molten
NaOH and Na in liquid2SO3Concentration be 0.05mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb 3 as solution medium 2, will
Graphene macroscopic material described in step one is added in reaction bulb 3 as catalyst filling 5, the addition of the catalyst filling 5
Measure and be：2g catalyst fillings 5 are added in every liter of solution medium 2, then the temperature of solution medium 2 are heated to using heater 4
72 DEG C, CO is utilized afterwards2Gas cylinder 11 is passed through CO into reaction bulb 32, and by flow control valve 10 by CO2Flow be adjusted to
150mL/min, finally opens uviol lamp 6, is 300 μ W/cm in the intensity of illumination of ultraviolet light2Under conditions of carry out photo catalytic reduction
CO2Processing, methanol is obtained in condensate liquid collecting tank 8.
The present embodiment uses anthracite to prepare graphene macroscopic material for raw material, and it has flourishing three-dimensional netted hole knot
Structure and multi-disc layer structure, in photo catalytic reduction CO2Substantial amounts of CO can be absorbed by preparing in the course of reaction of methanol2, improve
CO2Residence time of the gas in reaction system, be conducive to CO2Gas and catalyst and reaction medium are fully contacted；Secondly this
It is kind special it is mesh-structured unobstructed mass transfer channel is internally formed at it, provides good microenvironment and quickly for chemical reaction
The path of transfer charge；In addition, the oxygen-containing functional group not reduced thoroughly and active sites that graphene macroscopic material surface retains
Point, is also beneficial to improve its photocatalysis performance.The present embodiment uses graphene macroscopic material for photochemical catalyst, excellent catalytic effect,
High catalytic efficiency, methanol yield is high.
Embodiment 4
With reference to Fig. 1 to 3, the present embodiment carries out graphene macroscopic material photo catalytic reduction using equipment as described in Example 1
CO2The method for preparing methanol comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material, detailed process is：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of fine Coal
The microfine coal, is then placed in graphite crucible by powder, is incubated 2.5h under conditions of temperature is 2600 DEG C, obtains graphitization
Charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base oxidation
Graphene, detailed process is：By the concentrated sulfuric acid in mass ratio 1 that graphitized charcoal, sodium nitrate, potassium permanganate and mass concentration are 98%
: after 1: 5: 30 is well mixed, 10min is stirred under conditions of temperature is 0 DEG C, 30 DEG C of stirring 150min are then heated to, afterwards
It is warming up to after 90 DEG C and stirs 20min, after addition deionized water is diluted, uses the method for dropwise addition to add mass concentration for 30%
Hydrogen peroxide solution, carried out successively after stirring pickling, washing, filtering and drying process, obtain coal base graphene oxide；Institute
The addition for stating deionized water is 60 times of graphitized charcoal quality, and the addition of the hydrogen peroxide solution is the quality of potassium permanganate
It is equal；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, using electronation self-assembly method prepare
Coal base graphene hydrogel, detailed process is：The coal base graphene oxide is added into ultrasonic disperse in deionized water uniformly, to obtain
To coal base graphene oxide water solution, then the coal base graphene oxide water solution is well mixed with ethylenediamine and mixed
The mixed liquor, is incubated after 3h, natural cooling obtains coal base graphene hydrogel afterwards by liquid under conditions of temperature is 90 DEG C；
The concentration of the coal base graphene oxide water solution is the quality of coal base graphene oxide and ethylenediamine in 2g/L, the mixed liquor
Than for 0.2: 1；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be -55 DEG C under conditions of be freeze-dried
36h, obtains aeroge；
Step 105, under inert atmosphere protection, by aeroge described in step 104 with 5 DEG C/min heating rate liter
Temperature is made annealing treatment to constant temperature 1h after 850 DEG C, and coal base graphene macroscopic material is obtained after natural cooling；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3Mixing is molten
NaOH and Na in liquid2SO3Concentration be 0.1mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb 3 as solution medium 2, will
Graphene macroscopic material described in step one is added in reaction bulb 3 as catalyst filling 5, the addition of the catalyst filling 5
Measure and be：5g catalyst fillings 5 are added in every liter of solution medium 2, then the temperature of solution medium 2 are heated to using heater 4
68 DEG C, CO is utilized afterwards2Gas cylinder 11 is passed through CO into reaction bulb 32, and by flow control valve 10 by CO2Flow be adjusted to
50mL/min, finally opens uviol lamp 6, is 500 μ W/cm in the intensity of illumination of ultraviolet light2Under conditions of carry out photo catalytic reduction
CO2Processing, methanol is obtained in condensate liquid collecting tank 8.
The present embodiment uses anthracite to prepare graphene macroscopic material for raw material, and it has flourishing three-dimensional netted hole knot
Structure and multi-disc layer structure, in photo catalytic reduction CO2Substantial amounts of CO can be absorbed by preparing in the course of reaction of methanol2, improve
CO2Residence time of the gas in reaction system, be conducive to CO2Gas and catalyst and reaction medium are fully contacted；Secondly this
It is kind special it is mesh-structured unobstructed mass transfer channel is internally formed at it, provides good microenvironment and quickly for chemical reaction
The path of transfer charge；In addition, the oxygen-containing functional group not reduced thoroughly and avtive spot that graphene macroscopic material surface retains,
It is also beneficial to improve its photocatalysis performance.The present embodiment uses graphene macroscopic material for photochemical catalyst, excellent catalytic effect, catalysis
Efficiency high, methanol yield is high.
Embodiment 5
With reference to Fig. 1 to 3, the present embodiment carries out graphene macroscopic material photo catalytic reduction using equipment as described in Example 1
CO2The method for preparing methanol comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material, detailed process is：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of fine Coal
The microfine coal, is then placed in graphite crucible by powder, is incubated 3.5h under conditions of temperature is 2400 DEG C, obtains graphitization
Charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base oxygen
Graphite alkene, detailed process is：Graphitized charcoal, sodium nitrate, potassium permanganate and mass concentration are pressed into quality for 98% concentrated sulfuric acid
After more well mixed than 1: 0.5: 5: 40,50min is stirred under conditions of temperature is 20 DEG C, 40 DEG C of stirrings are then heated to
100min, is warming up to after 100 DEG C and stirs 10min afterwards, after addition deionized water is diluted, and matter is added using the method for dropwise addition
The hydrogen peroxide solution that concentration is 30% is measured, pickling, washing, filtering and drying process is carried out after stirring successively, obtains coal base
Graphene oxide；The addition of the deionized water is 40 times of graphitized charcoal quality, the addition of the hydrogen peroxide solution with
The quality of potassium permanganate is equal；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, using electronation self-assembly method prepare
Coal base graphene hydrogel, detailed process is：The coal base graphene oxide is added into ultrasonic disperse in deionized water uniformly, to obtain
To coal base graphene oxide water solution, then the coal base graphene oxide water solution is well mixed with ethylenediamine and mixed
The mixed liquor, is incubated after 8h, natural cooling obtains coal base graphene water-setting afterwards by liquid under conditions of temperature is 120 DEG C
Glue；The concentration of the coal base graphene oxide water solution is coal base graphene oxide and ethylenediamine in 6g/L, the mixed liquor
Mass ratio is 0.75: 1；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be -15 DEG C under conditions of be freeze-dried
48h, obtains aeroge；
Step 105, under inert atmosphere protection, by aeroge described in step 104 with 10 DEG C/min heating rate liter
Temperature is made annealing treatment to constant temperature 4h after 850 DEG C, and coal base graphene macroscopic material is obtained after natural cooling；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3Mixing is molten
NaOH and Na in liquid2SO3Concentration be 0.15mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb 3 as solution medium 2, will
Graphene macroscopic material described in step one is added in reaction bulb 3 as catalyst filling 5, the addition of the catalyst filling 5
Measure and be：0.5g catalyst fillings 5 are added in every liter of solution medium 2, then the temperature of solution medium 2 are heated using heater 4
To 72 DEG C, CO is utilized afterwards2Gas cylinder 11 is passed through CO into reaction bulb 32, and by flow control valve 10 by CO2Flow be adjusted to
150mL/min, finally opens uviol lamp 6, is 300 μ W/cm in the intensity of illumination of ultraviolet light2Under conditions of carry out photocatalysis also
Former CO2Processing, methanol is obtained in condensate liquid collecting tank 8.
The present embodiment uses anthracite to prepare graphene macroscopic material for raw material, and it has flourishing three-dimensional netted hole knot
Structure and multi-disc layer structure, in photo catalytic reduction CO2Substantial amounts of CO can be absorbed by preparing in the course of reaction of methanol2, improve
CO2Residence time of the gas in reaction system, be conducive to CO2Gas and catalyst and reaction medium are fully contacted；Secondly this
It is kind special it is mesh-structured unobstructed mass transfer channel is internally formed at it, provides good microenvironment and quickly for chemical reaction
The path of transfer charge；In addition, the oxygen-containing functional group not reduced thoroughly and avtive spot that graphene macroscopic material surface retains,
It is also beneficial to improve its photocatalysis performance.The present embodiment uses graphene macroscopic material for photochemical catalyst, excellent catalytic effect, catalysis
Efficiency high, methanol yield is high.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (8)
1. a kind of graphene macroscopic material photo catalytic reduction CO2The method for preparing methanol, it is characterised in that what this method was used sets
It is standby to include being provided with setting in multiple uviol lamps (6), the reaction chamber (1) on reaction chamber (1), the inwall of the reaction chamber (1)
There is the reaction bulb (3) for containing solution medium (2), the bottom of the reaction bulb (3) is provided with for the solution medium
(2) heater (4) heated, the top of the reaction bulb (3) is connected with condenser pipe (7), the condenser pipe (7) and condensation
Liquid collecting tank (8) is connected, and the bottom of the reaction bulb (3) passes through CO2Pipeline (9) is with being located at the CO of reaction chamber (1) outside2Gas cylinder
(11) connect, be provided with the reaction bulb (3) on porous barrier (12), the porous barrier (12) and be provided with catalyst filling
(5), the CO2Flow control valve (10) is provided with pipeline (9)；
Graphene macroscopic material photo catalytic reduction CO is carried out using the equipment2The method for preparing methanol comprises the following steps：
Step 1: using anthracite to prepare graphene macroscopic material for raw material；
Step 2: using deionized water to prepare NaOH-Na for solvent2SO3Mixed solution, the NaOH-Na2SO3In mixed solution
NaOH and Na2SO3Concentration be 0.05mol/L~0.15mol/L；
Step 3: by NaOH-Na described in step 22SO3Mixed solution is added in reaction bulb (3) as solution medium (2), will
Graphene macroscopic material described in step one is added in reaction bulb (3) as catalyst filling (5), then utilizes heater (4)
The temperature of solution medium (2) is heated to 68 DEG C~72 DEG C, CO is utilized afterwards2Gas cylinder (11) is passed through CO into reaction bulb (3)2, and
By flow control valve (10) by CO2Flow be adjusted to 50mL/min~150mL/min, finally open uviol lamp (6), ultraviolet
The intensity of illumination of light is 300 μ W/cm2~500 μ W/cm2Under conditions of carry out photo catalytic reduction CO2Processing, in condensate liquid collecting tank
(8) methanol is obtained in.
2. graphene macroscopic material photo catalytic reduction CO according to claim 12The method for preparing methanol, it is characterised in that：
The reaction chamber (1) is closed at both ends columnar structured, and the quantity of the uviol lamp (6) is six, six uviol lamps
(6) uniform ring cloth is on the inwall of reaction chamber (1).
3. graphene macroscopic material photo catalytic reduction CO according to claim 12The method for preparing methanol, it is characterised in that：
The material of the reaction bulb (3) is quartz glass.
4. graphene macroscopic material photo catalytic reduction CO according to claim 12The method for preparing methanol, it is characterised in that：
Hole in the porous barrier (12) is circular port, and the aperture of the circular port is 0.5mm~1mm.
5. graphene macroscopic material photo catalytic reduction CO according to claim 12The method for preparing methanol, it is characterised in that
The detailed process for using anthracite to prepare graphene macroscopic material for raw material described in step one is：
Step 101, anthracite crushed successively, is sieved and ball-milling treatment, obtaining granularity D90≤ 20 μm of microfine coal, so
The microfine coal is placed in graphite crucible afterwards, 2.5h~3.5h is incubated under conditions of temperature is 2400 DEG C~2600 DEG C,
Obtain graphitized charcoal；
Step 102, using graphitized charcoal described in step 101 as presoma, using improvement Hummers methods prepare coal base graphite oxide
Alkene；
Step 103, using the graphene oxide of coal base described in step 102 as raw material, coal base is prepared using electronation self-assembly method
Graphene hydrogel；
Step 104, by the graphene of coal base described in step 103 hydrogel temperature be freeze under conditions of -55 DEG C~-15 DEG C it is dry
Dry 36h~48h, obtains aeroge；
Step 105, under inert atmosphere protection, by aeroge described in step 104 with 5 DEG C/min~10 DEG C/min heating speed
Rate is warming up to constant temperature 1h~4h after 550 DEG C~850 DEG C and made annealing treatment, and the macroscopical material of coal base graphene is obtained after natural cooling
Material.
6. graphene macroscopic material photo catalytic reduction CO according to claim 52The method for preparing methanol, it is characterised in that
Used described in step 102 improvement Hummers methods prepare the detailed process of coal base graphene oxide for：By graphitized charcoal, nitric acid
Sodium, potassium permanganate and mass concentration are 98% concentrated sulfuric acid in mass ratio 1: (0.5~1): 5: after (30~40) are well mixed,
Temperature be 0 DEG C~20 DEG C under conditions of stir 10min~50min, then heat to 30 DEG C~40 DEG C stirring 100min~
300min, is warming up to stirring 10min~20min after 90 DEG C~100 DEG C, after addition deionized water is diluted, using drop afterwards
Plus method add mass concentration be 30% hydrogen peroxide solution, carried out successively after stirring pickling, washing, filtering and drying
Processing, obtains coal base graphene oxide；The addition of the deionized water is 40~60 times of graphitized charcoal quality, the dioxygen
The addition of the aqueous solution is equal with the quality of potassium permanganate.
7. graphene macroscopic material photo catalytic reduction CO according to claim 52The method for preparing methanol, it is characterised in that
Used described in step 103 electronation self-assembly method prepare the detailed process of coal base graphene hydrogel for：By the coal base
Graphene oxide adds ultrasonic disperse in deionized water and uniformly, coal base graphene oxide water solution is obtained, then by the coal base
Graphene oxide water solution is well mixed with ethylenediamine obtains mixed liquor, is afterwards 90 DEG C~120 in temperature by the mixed liquor
Coal base graphene hydrogel is obtained after being incubated 3h~8h, natural cooling under conditions of DEG C；The coal base graphene oxide water solution
Concentration be 2g/L~6g/L, the mass ratio of coal base graphene oxide and ethylenediamine is (0.2~0.75) in the mixed liquor: 1.
8. graphene macroscopic material photo catalytic reduction CO according to claim 1 or 52The method for preparing methanol, its feature exists
In the addition of catalyst filling described in step 3 (5) is：0.5g~5g catalyst is added in every liter of solution medium (2) to fill out
Expect (5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510852300.7A CN105289421B (en) | 2015-11-28 | 2015-11-28 | Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510852300.7A CN105289421B (en) | 2015-11-28 | 2015-11-28 | Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105289421A CN105289421A (en) | 2016-02-03 |
| CN105289421B true CN105289421B (en) | 2017-09-05 |
Family
ID=55187646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510852300.7A Active CN105289421B (en) | 2015-11-28 | 2015-11-28 | Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105289421B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022119463A1 (en) * | 2020-12-02 | 2022-06-09 | Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego | Method and device for the photoinduced conversion of co2 to methanol |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819430B (en) * | 2016-03-16 | 2018-08-17 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of coal base graphene |
| CN108557816B (en) * | 2018-06-26 | 2022-02-01 | 武汉大学 | Preparation method of porous graphitized carbon with high specific surface area |
| CN111167455B (en) * | 2020-02-12 | 2022-12-13 | 上海第二工业大学 | Graphene-loaded cobalt-doped titanium dioxide photocatalyst and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8389958B2 (en) * | 2009-03-18 | 2013-03-05 | Duke University | Up and down conversion systems for production of emitted light from various energy sources |
| CN202844878U (en) * | 2012-08-30 | 2013-04-03 | 苏州晶能科技有限公司 | Visible light photocatalysis and purification structure |
| CN103833028B (en) * | 2013-12-31 | 2015-04-22 | 深圳粤网节能技术服务有限公司 | Preparation method for graphene and graphene oxide based on anthracite |
| CN103803538B (en) * | 2014-01-28 | 2015-11-04 | 上海交通大学 | The magnanimity method of coal-based graphene quantum dot |
| CN104445177B (en) * | 2014-12-16 | 2016-09-28 | 中国科学院宁波材料技术与工程研究所 | The preparation method of a kind of Graphene and Graphene |
| CN104667932B (en) * | 2015-01-21 | 2016-09-28 | 西安建筑科技大学 | The preparation of Graphene reinforcing and toughening permeability solid waste base catalyst and the application in hydrogen manufacturing |
| CN205146185U (en) * | 2015-11-28 | 2016-04-13 | 西安科技大学 | Light catalytic reduction CO2 fixed bed reaction unit |
-
2015
- 2015-11-28 CN CN201510852300.7A patent/CN105289421B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022119463A1 (en) * | 2020-12-02 | 2022-06-09 | Instytut Niskich Temperatur I Badan Strukturalnych Pan Im.W.Trzebiatowskiego | Method and device for the photoinduced conversion of co2 to methanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105289421A (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105289421B (en) | Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol | |
| CN108516548A (en) | A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition | |
| CN106669756B (en) | Nano-layered g-C3N4Preparation method of/Ag @ AgCl composite photocatalytic material | |
| CN103301860B (en) | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst | |
| CN110627065B (en) | Preparation method and application of jute-based nitrogen-containing porous carbon | |
| CN111205469B (en) | Ultramicropore zirconium-based metal organic framework material and preparation method and application thereof | |
| CN106732727A (en) | Hexagonal boron nitride modification graphitization nitridation carbon composite photocatalyst and its preparation method and application | |
| CN106076303B (en) | Graphene oxide/nano titania needle composite material and preparation method and application | |
| CN109395749A (en) | Oxyhalogen bismuth nano material, preparation method and application | |
| Yuan et al. | A high-efficiency solar water evaporation-photocatalysis system achieved by manipulating surface wettability and constructing heterojunction | |
| Yi et al. | Effect of microwave absorption properties and morphology of manganese dioxide on catalytic oxidation of toluene under microwave irradiation | |
| CN110327988A (en) | A kind of preparation and application of PCN-222 (Cu)/titanic oxide nano compound material | |
| CN109701577B (en) | Method for preparing porous graphite phase carbon nitride by using carbon nano tube as hard template | |
| CN109665525A (en) | A kind of preparation method of " dumbbell shape " iron nitrogen codope porous carbon | |
| Wang et al. | Enhanced optical absorption and pollutant adsorption for photocatalytic performance of three-dimensional porous cellulose aerogel with BiVO4 and PANI | |
| CN111514880A (en) | Preparation method and application of porous carbon nitride/europium vanadate Z-type photocatalyst | |
| CN110327905A (en) | A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base | |
| CN108273519A (en) | A kind of hollow wave shape cadmium sulfide photochemical catalyst and preparation method for hydrogen manufacturing | |
| CN108786924A (en) | A kind of Ni (OH)2The preparation method of/TpPa-2 materials | |
| CN112121857A (en) | Graphene and I-Composite modified BiOCOOH material, preparation method and application thereof | |
| CN109468709B (en) | Preparation method of graphene-doped Co3O4 mesoporous fiber | |
| CN114452998B (en) | Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material | |
| CN108620133B (en) | Preparation method and application of two-dimensional transverse polymer heterojunction visible light response catalytic hydrogen production material | |
| CN110510596A (en) | A kind of preparation and application of the biomass porous carbon material of nitrogen iron codope | |
| CN112892572B (en) | Au-PCN-CNT composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |