CN105642321B - A kind of nanometer of red phosphorus/graphene composite photocatalyst and preparation method thereof - Google Patents
A kind of nanometer of red phosphorus/graphene composite photocatalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 2
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- 230000002829 reductive effect Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention belongs to photocatalysis technology field more particularly to a kind of nanometer of red phosphorus/graphene composite photocatalysts；Further relate to a kind of preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst.Using red phosphorus as base stock nanometer red phosphorus/graphene composite photocatalyst is made by mechanical milling method and ultrasonic flotation method in the surface of nanometer red phosphorus particulate load to graphene by red phosphorus nanosizing by nanometer red phosphorus/graphene composite photocatalyst of the invention.It is an advantage of the invention that photocatalysis performance is good, visible light photocatalysis reductive water H2-producing capacity and visible light photocatalysis RhB decoloration performance are significantly increased compared with prior art.
Description
Technical field
The invention belongs to photocatalysis technology field more particularly to a kind of nanometer of red phosphorus/graphene composite photocatalysts；This hair
A kind of bright preparation method for further relating to above-mentioned nanometer red phosphorus/graphene composite photocatalyst.
Background technique
Photocatalysis technology is considered as one of the key technology for solving energy and environmental problem.Since 1972
Fujishima has found TiO2Since with photocatalytic cleavage water H2-producing capacity, obtained after more than 40 years development photocatalysis technologies
Great progress.Some novel visible photochemical catalyst such as BiVO4、InGaN、BaTaO2N、CuInxGa1-xSe2Deng also being opened
It issues and achieves excellent photocatalysis performance.The polynary photochemical catalyst complicated with these is compared, in recent years some ingredient letters
Single simple substance photochemical catalyst also results in extensive concern, including red phosphorus, elemental sulfur and pure boron etc..Red phosphorus is a kind of stabilization
Semiconductor material, its forbidden bandwidth is 1.7eV, and optical absorption ranges almost cover entire visible region, have both simultaneously
Properly split water into the conduction band and valence band current potential of hydrogen and oxygen, thus photocatalysis field red phosphorus be it is a kind of have open by force very much
Send out the semiconductor material of potentiality.
Wang etc. reports the visible light photocatalysis reductive water H2-producing capacity of red phosphorus for the first time, and passes through density functional theory
Calculate the potential position of red phosphorus conduction band and valence band.Later, Wang etc. is prepared for Hierarchical P by hydro-thermal method4/
YPO4Microsphere composite photo-catalyst.The study found that the specific surface area of red phosphorus is increased after Y-ion hydro-thermal process
Greatly, while red phosphorus and YPO4The Heterojunction Effect formed between interface can effectively improve the separative efficiency in its light induced electron and hole.
Yuan etc. is by g-C3N4Layer is coated to the surface of red phosphorus, is prepared for Red phosphor/g-C3N4Heterojunction photocatalyst is ground
Study carefully discovery and works as g-C3N4When shared mass ratio reaches 30%, the photo catalytic reduction aquatic products hydrogen and light of the composite material can be significantly improved
It is catalyzed CO2Reducing property.Xia etc. has studied light of the red phosphorus under visible light and even sunlight excitation and urges
Change anti-microbial property, oxygen species (OH, the O generated under illumination excitation by research discovery red phosphorus2-, H2O2) can
To aoxidize the cell membrane of E.coli, to achieve the purpose that antibacterial.
However from the point of view of current progress, red phosphorus photocatalysis performance is limited to following two key factor: first party
The problem of face is that the partial size of the red phosphorus currently used for photocatalysis field is existed in the form of large-sized, this partial size state meeting
The surface photocatalytic activity number of loci for reducing red phosphorus, to limit the promotion of its photocatalysis performance；Second aspect, due to red phosphorus
Semiconducting crystal degree is lower, while its surface has a large amount of oxidation residual bond, so that its electron mobility is low, to increase
The probability of recombination again of light induced electron and hole.Therefore, the electron mobility of red phosphorus photochemical catalyst how is promoted, and exploitation is simply
Means prepare nanoscale red phosphorus photochemical catalyst and be of great significance.
Summary of the invention
An object of the present invention is to provide a kind of nanometer of red phosphorus/graphene composite photocatalyst, and photocatalysis performance is good,
And visible light photocatalysis reductive water H2-producing capacity and visible light photocatalysis RhB decoloration performance have compared with prior art it is aobvious
It writes and improves.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme: a kind of nanometer of red phosphorus/graphene complex light
Catalyst, using red phosphorus as base stock, by mechanical milling method and ultrasonic flotation method by red phosphorus nanosizing, by nanometer red phosphorus particle
The surface of graphene is loaded to, nanometer red phosphorus/graphene composite photocatalyst is made.
Further, the additive amount of the graphene is 10wt%-40wt%.
Preferably, the additive amount of the graphene is 20wt%.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst,
This nanometer of red phosphorus/graphene composite photocatalyst preparation method the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g quotient
It is annealed 4 hours for 400 DEG C under nitrogen protection with red phosphorus, then the red phosphorus is ground into 12h by 200r/Min in ball mill, after grinding
Red phosphorus ultrasonic disperse in ethanol, centrifugation goes 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, load weighted graphene oxide and nanometer is red
Phosphorus ultrasonic disperse is in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, washing, dry nanometer red phosphorus/graphene
Composite photo-catalyst.
For two key factors that red phosphorus photocatalysis performance in the prior art is limited in the present invention, red phosphorus is unfolded to be modified
Modify work.Since red phosphorus is the material of a kind of relatively " soft ", the present invention passes through mechanical milling method and ultrasonic flotation method
The mode combined prepares the red phosphorus (NRP) of Nano grade, achievees the purpose that promote red phosphorus light responsive surface active site.Stone
Black alkene is a kind of two-dimensional material with high electron mobility, at present a large number of studies show that, when graphene and semiconductor material are multiple
After conjunction, on the one hand by interface light induced electron metastasis, the electron transfer capabilities of photochemical catalyst can be remarkably reinforced in graphene, together
When graphene can promote the separative efficiency in semiconductor light-catalyst light induced electron and hole.
The method comprises the steps of firstly, preparing nanometer red phosphorus particles, will can effectively improve its specific surface area after red phosphorus nanosizing and light is urged
Change reactivity site, to improve its photocatalysis performance.Later by the surface of nanometer red phosphorus particulate load to graphene, preparation
Nanometer red phosphorus/graphene (NRP/G) composite photo-catalyst.Photocatalytic of the additive amount of graphene to the compound system material
It can have a major impact, when the additive amount of graphene reaches 20wt%, nanometer red phosphorus/graphene (NRP/G) composite photo-catalyst
With optimal photocatalysis performance, under visible light illumination, photo catalytic reduction water hydrogen-producing speed is about 65 μm of ol/g/h, compared with
NRP improves about 3 times, meanwhile, the photocatalysis RhB decoloration performance of the sample has also obtained significantly improving, can in 3Min
It realizes the complete decoloration to RhB, improves 5 times compared with NRP.Show to cause NRP/G composite photo-catalyst photocatalytic after study
The reason of capable of improving, the light induced electron that NRP is generated can quickly be infused along the reclinate conduction band of NRP mainly under illumination excitation
Enter onto graphene, and quickly transfer is occurred by the higher electron mobility of graphene, while photohole is then with opposite
Slower speed is transferred to the surface of red phosphorus, and the redox reaction in light induced electron and hole is respectively occurring at graphene and red phosphorus
On, thus light induced electron and the re-compounded probability of hole generation are effectively reduced, improve photocatalysis performance.
Compared with prior art, the beneficial effects of the present invention are:
(1) partial size of commercial red phosphorus can be reduced to Nano grade by mechanical lapping and ultrasonic flotation method by the present invention,
Preparation method is simple；By the way that these nanometer of grade red phosphorus to be loaded to the surface of graphene, supported nano red phosphorus/graphene is formed
Composite photo-catalyst optimizes light-catalyzed reaction active site, and improves the ability of light induced electron migration, separation.
(2) under illumination excitation, the light induced electron that NRP is generated can be rapidly injected stone along the reclinate conduction band of NRP
On black alkene, and quickly transfer is occurred by the higher electron mobility of graphene, while photohole is then with relatively slow
Speed is transferred to the surface of red phosphorus, and the redox reaction in light induced electron and hole is respectively occurring on graphene and red phosphorus, because
And light induced electron and the re-compounded probability of hole generation are effectively reduced, improve NRP/G composite photo-catalyst photocatalysis
Performance.
Detailed description of the invention
Fig. 1 is nanometer red phosphorus and nanometer red phosphorus/graphene composite photocatalyst SEM pattern；
Wherein, Figure 1A is the high-resolution SEM pattern of nanometer red phosphorus, and Figure 1B is that nanometer red phosphorus/graphene of embodiment 1 is multiple
The SEM pattern of light combination catalyst sample (NRP/G 10), Fig. 1 C are nanometer red phosphorus/graphene composite photocatalyst of embodiment 2
The SEM pattern of sample (NRP/G 20), Fig. 1 D are nanometer red phosphorus/graphene composite photocatalyst sample (NRP/G of embodiment 4
40) SEM pattern；
Fig. 2 is nanometer red phosphorus/graphene composite photocatalyst (NRP/G 20) sample Elemental redistribution test knot of embodiment 2
Fruit；
Fig. 3 A is nanometer red phosphorus/graphene composite photocatalyst (NRP/G 20) sample low power TEM pattern of embodiment 2
Figure, Fig. 3 B are the partial enlargement TEM pattern of Fig. 3 A, and Fig. 3 C is nanometer red phosphorus/graphene composite photocatalyst of embodiment 2
TEM shape appearance figure of (NRP/G 20) sample under higher magnification, Fig. 3 D are the partial enlargement TEM pattern of Fig. 3 C；
Fig. 4 is nanometer red phosphorus/graphene composite photocatalyst (NRP/G 20) sample XPS result of embodiment 2；
Wherein, Fig. 4 A is nanometer red phosphorus/graphene composite photocatalyst sample measurement result of embodiment 2, and Fig. 4 B is C
The XPS of 1s is as a result, Fig. 4 C is the XPS of P 2p as a result, the XPS result that Fig. 4 D is O 1s；
Fig. 5 is the nitrogen adsorption desorption BET result of NRP, NRP/G 10,40 4 NRP/G 20, NRP/G samples；
Fig. 6 is the graphite of the Different adding amount of commercial red phosphorus (RP), nanometer red phosphorus (NRP) and embodiment 1- embodiment 4
Alkene modifies photo catalytic reduction water H2-producing capacity of the sample under excited by visible light；
Fig. 7 A is the graphite of the Different adding amount of commercial red phosphorus (RP), nanometer red phosphorus (NRP) and embodiment 1- embodiment 4
The NRP sample photocatalysis RhB dyestuff degradation property of alkene modification；
Fig. 7 B is that 20 sample of NRP/G recycles decolorization experiment result to the photocatalysis of RhB.
Specific embodiment
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method is unless otherwise specified conventional method.
Embodiment 1
A kind of nanometer of red phosphorus/graphene composite photocatalyst passes through mechanical milling method and ultrasound using red phosphorus as base stock
Nanometer red phosphorus/graphene complex light is made in the surface of nanometer red phosphorus particulate load to graphene by red phosphorus nanosizing by floatation
Catalyst, the weight percent of the graphene are 10wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g quotient
It is annealed 4 hours for 400 DEG C under nitrogen protection with red phosphorus, then the red phosphorus is ground into 12h by 200r/Min in ball mill, after grinding
Red phosphorus ultrasonic disperse in ethanol, centrifugation goes 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, load weighted graphene oxide and nanometer is red
Phosphorus ultrasonic disperse is in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, washing, dry nanometer red phosphorus/graphene
Composite photo-catalyst.
Embodiment 2
A kind of nanometer of red phosphorus/graphene composite photocatalyst passes through mechanical milling method and ultrasound using red phosphorus as base stock
Nanometer red phosphorus/graphene complex light is made in the surface of nanometer red phosphorus particulate load to graphene by red phosphorus nanosizing by floatation
Catalyst, the weight percent of the graphene are 20wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g quotient
It is annealed 4 hours for 400 DEG C under nitrogen protection with red phosphorus, then the red phosphorus is ground into 12h by 200r/Min in ball mill, after grinding
Red phosphorus ultrasonic disperse in ethanol, centrifugation goes 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, load weighted graphene oxide and nanometer is red
Phosphorus ultrasonic disperse is in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, washing, dry nanometer red phosphorus/graphene
Composite photo-catalyst.
Embodiment 3
A kind of nanometer of red phosphorus/graphene composite photocatalyst passes through mechanical milling method and ultrasound using red phosphorus as base stock
Nanometer red phosphorus/graphene complex light is made in the surface of nanometer red phosphorus particulate load to graphene by red phosphorus nanosizing by floatation
Catalyst, the weight percent of the graphene are 30wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g quotient
It is annealed 4 hours for 400 DEG C under nitrogen protection with red phosphorus, then the red phosphorus is ground into 12h by 200r/Min in ball mill, after grinding
Red phosphorus ultrasonic disperse in ethanol, centrifugation goes 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, load weighted graphene oxide and nanometer is red
Phosphorus ultrasonic disperse is in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, washing, dry nanometer red phosphorus/graphene
Composite photo-catalyst.
Embodiment 4
A kind of nanometer of red phosphorus/graphene composite photocatalyst passes through mechanical milling method and ultrasound using red phosphorus as base stock
Nanometer red phosphorus/graphene complex light is made in the surface of nanometer red phosphorus particulate load to graphene by red phosphorus nanosizing by floatation
Catalyst, the weight percent of the graphene are 40wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g quotient
It is annealed 4 hours for 400 DEG C under nitrogen protection with red phosphorus, then the red phosphorus is ground into 12h by 200r/Min in ball mill, after grinding
Red phosphorus ultrasonic disperse in ethanol, centrifugation goes 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, load weighted graphene oxide and nanometer is red
Phosphorus ultrasonic disperse is in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, washing, dry nanometer red phosphorus/graphene
Composite photo-catalyst.
Experimental result
Fig. 1 is the SEM pattern of the NRP sample of nanometer red phosphorus and Different adding amount graphene modified, can be with from Figure 1A
It learns, a large amount of partial size is less than the red phosphorus particle packing of 100nm together, and from Figure 1A, not it is observed that partial size is greater than
The particle of micron level shows that the mechanical lapping and ultrasonic flotation method in through the invention can reduce the partial size of commercial red phosphorus
To Nano grade.Figure 1B is that (i.e. the additive amount of graphene is for nanometer red phosphorus/graphene composite photocatalyst of embodiment 1
Nanometer red phosphorus/graphene composite photocatalyst, hereinafter referred to as NRP/G 10 of 10wt%) sample SEM pattern.From Figure 1B
Other than being observed that a large amount of nano particles, it can also be observed that there is a small amount of flaky substance, illustrate graphene
It is combined in NRP.Fig. 1 C is that (i.e. the additive amount of graphene is for nanometer red phosphorus/graphene composite photocatalyst of embodiment 2
Nanometer red phosphorus/graphene composite photocatalyst, hereinafter referred to as NRP/G 20 of 20wt%) sample SEM pattern.Comparison diagram 1C
With Figure 1B it can be found that as there is one layer of cladding substance, explanation in the promotion red phosphorus nano grain surface of graphene additive amount
The compound quantity for increasing graphene can form uniform NRP/G supporting structure.Fig. 1 D is (the i.e. additive amount of graphene of NRP/G 40
For nanometer red phosphorus/graphene composite photocatalyst, hereinafter referred to as NRP/G 40 of 40wt%) the SEM pattern of sample, from Fig. 1 D
Result it is known that with graphene additive amount further promotion, red phosphorus particle covers by thick graphene layer,
Therefore the exposed surface in composite material of a small amount of red phosphorus particle can only be observed.
In order to further test the Elemental redistribution in composite material, we have carried out Elemental redistribution survey to 20 sample of NRP/G
It tries (element mapping), correlated results is as shown in Figure 2.The wire marked region having chosen in Fig. 2A carries out Elemental redistribution
It tests (element mapping).By test find, the area distribution P element and C element, this meets 20 sample of NRP/G
The element of product forms, and it is compound to illustrate that red phosphorus and graphene have occurred really.
In order to further characterize the microstructure between graphene and red phosphorus, by transmission electron microscope (TEM) to implementation
The nanometer red phosphorus of example 2/graphene composite photocatalyst (NRP/G 20) sample is tested, and corresponding test result is as schemed
Shown in 3A- Fig. 3 D.Fig. 3 A is the low power TEM shape appearance figure of 20 sample of NRP/G, is observed that a large amount of flaky substance from Fig. 3 A
In the presence of, while other materials are dispersed on these flaky substance surfaces.In order to observe the micro Distribution of 20 sample of NRP/G
Structure selects local location in Fig. 3 A to be exaggerated, and accordingly result is as shown in Figure 3B, can obviously observe from Fig. 3 B big
Small red phosphorus even particulate dispersion is measured in the graphene-structured of sheet, forms loaded composite construction.Fig. 3 C is
TEM shape appearance figure of 20 sample of NRP/G under higher magnification, it can be observed that the partial size of red phosphorus mainly divides from the picture
Cloth 100nm hereinafter, only a small amount of red phosphorus grain diameter between 100 between 200nm, which can confirm reality of the invention
The red phosphorus particle for the Nano grade that the means of testing can be prepared.Fig. 3 D is the partial enlargement TEM pattern of Fig. 3 C, can be with from the result
It learns, nanometer red phosphorus (NRP) and graphene (graphene) can occur closely to contact, this may be to be due to graphene table
The existing oxidation residual bond in face and the micro-oxidation group on red phosphorus surface are combined, thus the two can be combined closely one
It rises, forms excellent electron-transport interface.
Fig. 4 is the XPS of 20 sample of NRP/G as a result, by the test of XPS, needs to obtain the elemental composition information of the sample
And each element surface chemical state information.Fig. 4 A is the measurement result of 20 sample of NRP/G, can learn this from the figure
Sample is made of tri- kinds of elements of P, C, O.Fig. 4 B is the XPS of C 1s as a result, can learn that 284.5eV corresponds to stone from the result
The C-C key characteristic peak of black alkene, 286.6eV correspond to the peak C-O, illustrate that graphene is not completely reduced, surface still remains one
Fixed C-O residual bond.Fig. 4 C is the XPS of P 2p as a result, wherein 130.2eV corresponds to the characteristic peak of NRP, and 134.5eV corresponds to NRP
The oxide group characteristic peak on surface shows that there are certain oxidation residual bonds on the surface NRP.Fig. 4 D is the XPS of O 1s as a result, to the knot
It is known that the appearance at 532.5eV corresponds to the characteristic peak of O-C key after fruit progress swarming, and the appearance at 533.7eV is corresponding
Positive PO4 3-Characteristic peak.Result above is summarized it is known that in 20 sample of NRP/G, NRP and graphene surface all have one
Fixed oxidation residual bond, and these aoxidize the residual bonds combination alternate to the distribution of nanometer red phosphorus and two and have certain contribution work
With.
Fig. 5 is the nitrogen adsorption desorption BET result of NRP, NRP/G 10,40 4 NRP/G 20, NRP/G samples.From four samples
From the point of view of the nitrogen adsorption desorption isothermal curve shape of product, do not occur apparent meso-hole structure in sample, and works as P/P0More than 0.9 with
Afterwards, the existing apparent rising of adsorbance (Volume Adsorbed) numerical value of 20, three NRP, NRP/G 10, NRP/G samples, this
Be due to accumulation existing between red phosphorus nano particle hole caused by.But for this sample of NRP/G 40, in the region
Interior adsorbance (Volume Adsorbed) numerical value is not obviously improved, should be the result shows that when graphene additive amount improves
After to a certain extent, the gap between NRP can be clogged, thus do not observe the presence in accumulation hole, it should in the result and Fig. 1 D
The SEM of sample shows that pattern is corresponding.The reference area numerical value that 4 samples are inserted in Fig. 5, comparing these numerical value can send out
Existing, the specific surface area of sample is gradually increased with the raising of graphene additive amount, this is mainly that graphene has huge ratio
Caused by surface area, the addition of surface graphene may provide side to adsorption process early period during NRP/G composite photocatalyst
It helps.
In order to characterize the compound influence to NRP photocatalysis performance of graphene, RP, NRP, NRP/G10, NRP/G are tested
20, NRP/G 30 (i.e. the additive amount of graphene obtained by embodiment 3 be 30wt% nanometer red phosphorus/graphene complex light urge
Agent) and photo catalytic reduction water H2-producing capacity of 40 sample of NRP/G under excited by visible light, the testing time of each sample
Respectively 1 hour, reaction solution was triethanolamine solution, and corresponding test results are shown in figure 6.It can be obtained from the result
Know, large-sized commercialization red phosphorus (RP) Photocatalyzed Hydrogen Production efficiency is minimum, and 1 hour hydrogen output is about 9 μm of ol/g/h, this is mainly
Commercial red phosphorus grain diameter is very big, and light-catalyzed reaction active site is few, while a large amount of light induced electrons and hole are in its body Xiang Zhongfa
It has given birth to compound.After commercial red phosphorus nanosizing is prepared into a nanometer red phosphorus (NRP), Photocatalyzed Hydrogen Production amount is increased to 20 μm of ol/g/
H, more commercial RP are doubled, this may be due to Nano grade red phosphorus have more light-catalyzed reaction active sites,
And the diminution of partial size reduces the distance that light induced electron is transmitted from the opposite surface of material bodies, to reduce light induced electron and sky
Re-compounded probability occurs for cave.The addition of graphene has great influence to the photocatalysis performance of NRP/G.When graphene is compound
When amount is 10wt%, the Photocatalyzed Hydrogen Production performance boost of 10 sample of NRP/G to about 41 μm of ol/g/h.When the compound quantity of graphene
When continuing to be increased to 20wt%, Photocatalyzed Hydrogen Production efficiency is further increased to 65 μm of ol/g/h.Later, as graphene is compound
Amount further increases, and photocatalysis performance is in rapid decrease trend.When the compound quantity of graphene is increased to 40wt%, light is urged
Change hydrogen output and is reduced to about 19 μm of ol/g/h.The above result shows that the photocatalysis when the compound quantity of graphene is less, to NRP
Performance has apparent facilitation.And the mechanism for causing the performance boost may be since graphene promotes NRP photoproduction electricity
The transfer and separative efficiency of son and hole, to improve its photo catalytic reduction water H2-producing capacity.
In order to further characterize the influence of nanosizing and graphene modified to the photocatalysis performance of red phosphorus, further survey
40 photocatalysis RhB dyestuff degradation property of RP, NRP, NRP/G 10, NRP/G 20, NRP/G 30 and NRP/G is tried.Fig. 7 A is
The photocatalysis performance of the NRP sample of commercial red phosphorus (RP), nanometer red phosphorus (NRP) and Different adding amount graphene modified.Dark
After stirring 30Min under state, it can be found that there are apparent differences for adsorption capacity of these samples to RhB.Commercial red phosphorus is to dyestuff
Adsorption capacity it is most weak, but by after commercial red phosphorus nanosizing, it can be found that the adsorption capacity of NRP occurs on obviously
It rises, in 30Min, almost there is 65% RhB to be adsorbed by it, this is mainly due to the specific surface areas of the more commercial red phosphorus of NRP to have
Caused by being obviously improved.After with the raising of the addition of graphene, the Dye Adsorption performance of NRP/G composite photo-catalyst occurs
Small size promotion, but when graphene additive amount is increased to 40wt%, which occurs one
Jumping, the RhB of about 80wt% is absorbed within half an hour.The above phenomenon explanation, is answered by red phosphorus nanosizing or by graphene
Modification is closed, its adsorption capacity to RhB can be improved.After 30Min to be adsorbed, serial sample is tested under the conditions of visible light shines
The photocatalytic degradation capability of product.From Fig. 7 A it can be found that for commercial red phosphorus, by the illumination of 30Min, the sample can be right
About 85% RhB realizes decoloration.However the NRP after commercial red phosphorus nanosizing, being prepared can be realized pair in 15Min
The complete decoloration of RhB, after illustrating nanosizing, the light-catalyzed reaction active site of NRP be increased significantly.By different amounts of graphene
After compound, there is apparent variation, NRP/G compared with NRP in the photocatalysis RhB degradation property of obtained NRP/G composite photo-catalyst
10 can realize the complete decoloration to RhB in 10Min.When graphene, which is added to, is increased to 20wt%, the light of NRP/G 20
Apparent raising has occurred in catalysis RhB performance, and the complete decoloration to RhB can be realized in about 3Min.Later with graphene
Additive amount further increases, the photocatalysis RhB degradation property of NRP/G 30 return to the comparable level of NRP, and work as graphene
After additive amount is increased to 40wt%, the photocatalysis RhB decoloration performance of NRP/G 40 almost disappears.The above photocatalysis performance tests table
It is bright, when graphene additive amount is less, the photocatalysis performance of composite photo-catalyst can be significantly improved, this may be due to graphite
The addition of alkene increases light induced electron separation and the transfer ability of NRP, to improve its photocatalysis RhB decoloration performance.But
After graphene additive amount reaches 4wt%, the reason of photocatalysis RhB decoloration performance is almost disappeared, causes the phenomenon
It is that 80% RhB has almost been adsorbed in 30Min since adsorption capacity of the NRP/G 40 to RhB is too strong, when a large amount of RhB is wrapped up
Behind 40 surface NRP/G, it will occur to compete extinction process with it, photon is mainly captured by RhB, and NRP/G 40 cannot be excited,
So that apparent reduction has occurred in the photocatalysis performance of NRP/G 40.Since NRP/G 20 has strongest photocatalytic
Can, we recycle decolorization experiment by the photocatalysis to RhB, and the absorption stability and Photocatalytic Decoloration for investigating the sample are stablized
Property, accordingly result is as shown in Figure 7 B.It, still can be it can be found that NRP/G 20 passes through 5 reaction cycles from the curve
3Min is implemented around the complete decoloration to RhB, and its adsorption capacity be also it is stable, recycle its adsorption capacity simultaneously by 5 times
Do not occur significantly decaying.The phenomenon shows that RhB has very strong absorption stability and photocatalysis stability.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, without departing from the principle of the present invention, several improvement can also be made, these improvement should be regarded as guarantor of the invention
Protect range.
Claims (3)
1. a kind of nanometer of red phosphorus/graphene composite photocatalyst, it is characterised in that: using red phosphorus as base stock, pass through mechanical grinding
Mill method and ultrasonic flotation method are by red phosphorus nanosizing, by the surface of nanometer red phosphorus particulate load to graphene, obtained nanometer red phosphorus/stone
Black alkene composite photo-catalyst, the additive amount of the graphene are 10wt%-40wt%.
2. according to claim 1 nanometer of red phosphorus/graphene composite photocatalyst, it is characterised in that: the graphene
Additive amount is 20wt%.
3. a kind of preparation method of nanometer red phosphorus/graphene composite photocatalyst of any of claims 1-2, special
Sign be the following steps are included:
(1) it prepares nanometer grade red phosphorus: preparing a nanometer grade red phosphorus by mechanical milling method and ultrasonic flotation method: 10g commercialization is red
Phosphorus is annealed 4 hours for 400 DEG C under nitrogen protection, then the red phosphorus is ground 12h by 200r/Min in ball mill, red after grinding
Ultrasonic disperse, centrifugation go 80 degree of upper layer suspension to be dried to obtain a nanometer red phosphorus to phosphorus in ethanol；
(2) graphene oxide is prepared by Hunmer method；
(3) graphene oxide obtained by step (2) is weighed according to the proportion, and load weighted graphene oxide and nanometer red phosphorus are surpassed
Sound is dispersed in 60mL water, and after being completely dispersed, 2h is irradiated under xenon lamp, is centrifuged, and washing is dry that nanometer red phosphorus/graphene is compound
Photochemical catalyst.
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| CN107598150B (en) * | 2017-08-15 | 2019-08-16 | 西北大学 | A kind of nano metal/red phosphorus composite material and preparation method |
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| CN108772079B (en) * | 2018-04-26 | 2021-03-02 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene composite material |
| CN109759098B (en) * | 2019-03-07 | 2021-11-19 | 郑州大学 | Nano red phosphorescent catalyst, preparation method and application in degradation of dye in water and photocatalytic water hydrogen production |
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| CN111203247A (en) * | 2020-02-24 | 2020-05-29 | 青岛旭晟东阳新材料有限公司 | Red phosphorus-based semiconductor antibacterial photocatalyst and preparation method thereof |
| CN112774703A (en) * | 2021-02-01 | 2021-05-11 | 北京工业大学 | Elemental red phosphorus-loaded titanium dioxide composite catalyst for efficient photocatalytic decomposition of water to produce hydrogen |
| CN114471640B (en) * | 2021-12-31 | 2024-03-29 | 北京工业大学 | Controllable preparation of compound crystal form three-dimensional dendritic red phosphorus single-substance photocatalyst and application of compound crystal form three-dimensional dendritic red phosphorus single-substance photocatalyst in hydrogen production by water splitting |
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