CN105642321A - Nano red phosphorus/graphene composite photocatalyst and preparation method thereof - Google Patents
Nano red phosphorus/graphene composite photocatalyst and preparation method thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 127
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005188 flotation Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003701 mechanical milling Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 46
- 238000007146 photocatalysis Methods 0.000 abstract description 36
- 239000002245 particle Substances 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract 2
- 229940043267 rhodamine b Drugs 0.000 abstract 2
- 238000000227 grinding Methods 0.000 abstract 1
- 238000007709 nanocrystallization Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
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- 239000000976 ink Substances 0.000 description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
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- 239000004575 stone Substances 0.000 description 2
- 229910002937 BaTaO2N Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
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- 238000003776 cleavage reaction Methods 0.000 description 1
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- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
Abstract
The invention belongs to the technical field of photocatalysis, particularly relates to a nano red phosphorus/graphene composite photocatalyst, and further relates to a preparation method of the nano red phosphorus/graphene composite photocatalyst. The nano red phosphorus/graphene composite photocatalyst disclosed by the invention is characterized in that red phosphorus is taken as a basic raw material; the red phosphorus is subjected to nanocrystallization by utilization of a mechanical grinding method and an ultrasonic flotation method; the nano red phosphorus/graphene composite photocatalyst is prepared by means of loading nano red phosphorus particles on the surface of graphene. The nano red phosphorus/graphene composite photocatalyst has the advantages that the effect of good photocatalytic performance is achieved, and the visible light photocatalytic-reducing hydrogen production performance and visible light photocatalytic RhB (Rhodamine B) decolorizing performance are significantly improved in comparison with the prior art.
Description
Technical field
The invention belongs to photocatalysis technology field, relate in particular to a kind of nanometer red phosphorus/graphene composite photocatalyst; ThisThe bright preparation method who also relates to a kind of above-mentioned nanometer red phosphorus/graphene composite photocatalyst.
Background technology
Photocatalysis technology is considered to one of key technology solving the energy and environmental problem. Since 1972Fujishima finds TiO2Since having photocatalytic cleavage aquatic products hydrogen performance, the development photocatalysis technology of going through more than 40 year is obtainedGreat progress. Some novel visible photochemical catalysts are as BiVO4、InGaN、BaTaO2N、CuInxGa1-xSe2Deng also being openedSend and obtained excellent photocatalysis performance. Compare and the polynary photochemical catalyst of these complexity some composition letters in recent yearsSingle simple substance photochemical catalyst has also caused widely to be paid close attention to, and comprises red phosphorus, elemental sulfur and pure boron etc. Red phosphorus is a kind of stableSemi-conducting material, its energy gap is 1.7eV, its optical absorption scope has almost contained whole visible region, has concurrently simultaneouslyTherefore suitable conduction band and the valence band current potential that splits water into hydrogen and oxygen be that one has very by force and opens at photocatalysis field red phosphorusSend out the semi-conducting material of potentiality.
The reported first such as Wang the visible light photocatalysis reduction aquatic products hydrogen performance of red phosphorus, and pass through density functional theoryCalculate the current potential position of red phosphorus conduction band and valence band. Afterwards, Wang etc. has prepared HierarchicalP by hydro-thermal method4/YPO4Microsphere composite photo-catalyst. Research discovery, after the heat treatment of Y ionized water, the specific area of red phosphorus is increasedRed phosphorus and YPO greatly, simultaneously4The Heterojunction Effect forming between interface can effectively improve the separative efficiency in its light induced electron and hole.Yuan etc. are by g-C3N4Layer is coated to the surface of red phosphorus, has prepared Redphosphor/g-C3N4Heterojunction photocatalyst, it grindsStudy carefully discovery and work as g-C3N4When shared mass ratio reaches 30%, can obviously improve photo catalytic reduction aquatic products hydrogen and the light of this compositeCatalysis CO2Reducing property. Xia etc. have studied the light of red phosphorus under visiblelightandevensunlight excites and have urgedChange anti-microbial property, find that by research red phosphorus excites oxygenspecies (OH, the O of lower generation in illumination2-，H2O2) canSo that the cell membrane of E.coli is oxidized, thereby reach antibacterial object.
But from current progress, red phosphor catalytic performance is limited to following two key factors: first partyThe problem of face is that the particle diameter of the current red phosphorus for photocatalysis field is all to exist with large-sized form, the meeting of this particle diameter stateThe surface light catalytic active site of reduction red phosphorus is counted out, thereby limits the lifting of its photocatalysis performance; Second aspect, due to red phosphorusSemiconducting crystal degree is lower, and its surface exists a large amount of oxidation residual bonds simultaneously, makes its electron mobility low, thereby has raiseThe probability of recombination again in light induced electron and hole. Therefore, how to promote the electron mobility of red phosphor catalyst, and develop simple and easyMeans to prepare nanoscale red phosphor catalyst significant.
Summary of the invention
One of object of the present invention is to provide a kind of nanometer red phosphorus/graphene composite photocatalyst, and its photocatalysis performance is good,And visible light photocatalysis reduction aquatic products hydrogen performance and visible light photocatalysis RhB decoloration performance compared with prior art all have aobviousWork improves.
In order to solve the problems of the technologies described above, the present invention by the following technical solutions: a kind of nanometer red phosphorus/Graphene complex lightCatalyst, taking red phosphorus as base stock, by mechanical milling method and ultrasonic flotation method by red phosphorus nanometer, by nanometer red phosphorus particleLoad to the surface of Graphene, make nanometer red phosphorus/graphene composite photocatalyst.
Further, the addition of described Graphene is 10wt%-40wt%.
Preferably, the addition of described Graphene is 20wt%.
Another object of the present invention is to provide a kind of preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst,The preparation method of this nanometer red phosphorus/graphene composite photocatalyst comprises the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g businessWith red phosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, after grindingRed phosphorus ultrasonic dispersion in ethanol, centrifugal, remove the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by red to load weighted graphene oxide and nanometerPhosphorus is ultrasonic to be dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing, is dried to obtain nanometer red phosphorus/GrapheneComposite photo-catalyst.
In the present invention, for two limited key factors of red phosphor catalytic performance in prior art, red phosphorus is launched to modificationModification work. Because red phosphorus is the relatively material of " soft " of one, therefore the present invention is by mechanical milling method and ultrasonic flotation methodThe mode combining, prepares the red phosphorus (NRP) of Nano grade, reaches the object that promotes red phosphorus light responsive surface avtive spot. StoneChina ink alkene is a kind of two-dimensional material with high electron mobility, and at present large quantity research shows, when Graphene and semi-conducting material multipleAfter closing, by interface light induced electron metastasis, Graphene can obviously strengthen the electron transfer ability of photochemical catalyst on the one hand, withTime Graphene can promote the separative efficiency in semiconductor light-catalyst light induced electron and hole.
First the present invention has prepared nanometer red phosphorus particle, will after red phosphorus nanometer, can effectively improve its specific area and light is urgedChange reactivity site, thereby improve its photocatalysis performance. The surface to Graphene by nanometer red phosphorus particulate load afterwards, preparationNanometer red phosphorus/Graphene (NRP/G) composite photo-catalyst. The photocatalytic of the addition of Graphene to this compound system materialCan there is material impact, in the time that the addition of Graphene reaches 20wt%, nanometer red phosphorus/Graphene (NRP/G) composite photo-catalystHave best photocatalysis performance, under radiation of visible light, its photo catalytic reduction water hydrogen-producing speed is about 65 μ mol/g/h,NRP has improved approximately 3 times, and meanwhile, the photocatalysis RhB decoloration performance of this sample has also obtained improving significantly, can in 3MinRealize the decolouring completely to RhB, improved 5 times compared with NRP. Show through research, cause NRP/G composite photo-catalyst photocatalyticThe reason that can improve is mainly under illumination excites, and the light induced electron that NRP produces can be noted fast along the reclinate conduction band of NRPEnter to Graphene, and occur to shift fast by the higher electron mobility of Graphene, photohole is with relatively simultaneouslySlower speed is transferred to the surface of red phosphorus, and the redox reaction in light induced electron and hole occurs in respectively Graphene and red phosphorusUpper, thereby effectively reduce light induced electron and re-compounded probability occurs in hole, improve photocatalysis performance.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention can be reduced to Nano grade by the particle diameter of commercial red phosphorus by mechanical lapping and ultrasonic flotation method,Preparation method is simple; By these nanoscale red phosphorus being loaded to the surface of Graphene, form supported nano red phosphorus/GrapheneComposite photo-catalyst, optimized light-catalyzed reaction avtive spot, and promoted the ability of light induced electron migration, separation.
(2), under illumination excites, the light induced electron that NRP produces can be injected into stone fast along the reclinate conduction band of NRPOn China ink alkene, and occur to shift fast by the higher electron mobility of Graphene, photohole is with relatively slow simultaneouslySpeed is transferred to the surface of red phosphorus, and the redox reaction in light induced electron and hole occurs in respectively on Graphene and red phosphorus, because ofAnd effectively reduce light induced electron and re-compounded probability occurs in hole, improve the photocatalysis of NRP/G composite photo-catalystPerformance.
Brief description of the drawings
Fig. 1 is the SEM pattern of nanometer red phosphorus and nanometer red phosphorus/graphene composite photocatalyst;
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 multipleClose the SEM pattern of photochemical catalyst sample (NRP/G10), Fig. 1 C is nanometer red phosphorus/graphene composite photocatalyst of embodiment 2The SEM pattern of sample (NRP/G20), Fig. 1 D is nanometer red phosphorus/graphene composite photocatalyst sample (NRP/G of embodiment 440) SEM pattern;
Fig. 2 is nanometer red phosphorus/graphene composite photocatalyst (NRP/G20) sample element distribution tests knot of embodiment 2Really;
Fig. 3 A is the low power TEM pattern of nanometer red phosphorus/graphene composite photocatalyst (NRP/G20) sample of embodiment 2Figure, Fig. 3 B is that TEM pattern is amplified in the part of Fig. 3 A, Fig. 3 C is nanometer red phosphorus/graphene composite photocatalyst of embodiment 2(NRP/G20) sample is at the TEM shape appearance figure compared with under high-amplification-factor, and Fig. 3 D is that TEM pattern is amplified in the part of Fig. 3 C;
Fig. 4 is the XPS result of nanometer red phosphorus/graphene composite photocatalyst (NRP/G20) sample of embodiment 2;
Wherein, Fig. 4 A is the measurement result of nanometer red phosphorus/graphene composite photocatalyst sample of embodiment 2, and Fig. 4 B is CThe XPS result of 1s, the XPS result that Fig. 4 C is P2p, the XPS result that Fig. 4 D is O1s;
Fig. 5 is the nitrogen adsorption desorption BET result of NRP, NRP/G10, NRP/G20, tetra-samples of NRP/G40;
Fig. 6 is the graphite of the Different adding amount of commercial red phosphorus (RP), nanometer red phosphorus (NRP) and embodiment 1-embodiment 4Alkene is modified the photo catalytic reduction aquatic products hydrogen performance of 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 4The NRP sample photocatalysis RhB dyestuff degradation property that alkene is modified;
Fig. 7 B is the photocatalysis circulation decolorization experiment result of NRP/G20 sample to RhB.
Detailed description of the invention
Following embodiment is convenient to understand better the present invention, but does not limit the present invention. Experiment in following embodimentMethod, if no special instructions, is conventional method.
Embodiment 1
A kind of nanometer red phosphorus/graphene composite photocatalyst, taking red phosphorus as base stock, by mechanical milling method and ultrasonicFloatation is by red phosphorus nanometer, and the surface by nanometer red phosphorus particulate load to Graphene, makes nanometer red phosphorus/Graphene complex lightCatalyst, the percentage by weight of described Graphene is 10wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst comprises the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g businessWith red phosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, after grindingRed phosphorus ultrasonic dispersion in ethanol, centrifugal, remove the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by red to load weighted graphene oxide and nanometerPhosphorus is ultrasonic to be dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing, is dried to obtain nanometer red phosphorus/GrapheneComposite photo-catalyst.
Embodiment 2
A kind of nanometer red phosphorus/graphene composite photocatalyst, taking red phosphorus as base stock, by mechanical milling method and ultrasonicFloatation is by red phosphorus nanometer, and the surface by nanometer red phosphorus particulate load to Graphene, makes nanometer red phosphorus/Graphene complex lightCatalyst, the percentage by weight of described Graphene is 20wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst comprises the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g businessWith red phosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, after grindingRed phosphorus ultrasonic dispersion in ethanol, centrifugal, remove the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by red to load weighted graphene oxide and nanometerPhosphorus is ultrasonic to be dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing, is dried to obtain nanometer red phosphorus/GrapheneComposite photo-catalyst.
Embodiment 3
A kind of nanometer red phosphorus/graphene composite photocatalyst, taking red phosphorus as base stock, by mechanical milling method and ultrasonicFloatation is by red phosphorus nanometer, and the surface by nanometer red phosphorus particulate load to Graphene, makes nanometer red phosphorus/Graphene complex lightCatalyst, the percentage by weight of described Graphene is 30wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst comprises the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g businessWith red phosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, after grindingRed phosphorus ultrasonic dispersion in ethanol, centrifugal, remove the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by red to load weighted graphene oxide and nanometerPhosphorus is ultrasonic to be dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing, is dried to obtain nanometer red phosphorus/GrapheneComposite photo-catalyst.
Embodiment 4
A kind of nanometer red phosphorus/graphene composite photocatalyst, taking red phosphorus as base stock, by mechanical milling method and ultrasonicFloatation is by red phosphorus nanometer, and the surface by nanometer red phosphorus particulate load to Graphene, makes nanometer red phosphorus/Graphene complex lightCatalyst, the percentage by weight of described Graphene is 40wt%.
The preparation method of above-mentioned nanometer red phosphorus/graphene composite photocatalyst comprises the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by 10g businessWith red phosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, after grindingRed phosphorus ultrasonic dispersion in ethanol, centrifugal, remove the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by red to load weighted graphene oxide and nanometerPhosphorus is ultrasonic to be dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing, is dried to obtain nanometer red phosphorus/GrapheneComposite 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 from Figure 1ALearn, the red phosphorus particle packing that a large amount of particle diameters is less than 100nm together, and from Figure 1A, can not be observed particle diameter and be greater thanThe particle of micron level, shows the particle diameter of commercial red phosphorus to be reduced by the mechanical lapping in the present invention and ultrasonic flotation methodTo Nano grade. Figure 1B is that (addition that is Graphene is for nanometer red phosphorus/graphene composite photocatalyst of embodiment 1Nanometer red phosphorus/graphene composite photocatalyst of 10wt%, is designated hereinafter simply as NRP/G10) the SEM pattern of sample. From Figure 1BExcept observing a large amount of nano particles, can also observe and occur a small amount of flaky substance, illustrate that Graphene isBe compound in NRP. Fig. 1 C is that (addition that is Graphene is for nanometer red phosphorus/graphene composite photocatalyst of embodiment 2Nanometer red phosphorus/graphene composite photocatalyst of 20wt%, is designated hereinafter simply as NRP/G20) the SEM pattern of sample. Comparison diagram 1CCan find with Figure 1B, along with the lifting red phosphorus nano grain surface of Graphene addition has occurred that one deck is coated material, explanationThe compound quantity that increases Graphene can form uniform NRP/G and support structure. Fig. 1 D is that NRP/G40 (is the addition of GrapheneFor nanometer red phosphorus/graphene composite photocatalyst of 40wt%, be designated hereinafter simply as NRP/G40) the SEM pattern of sample, from Fig. 1 DResult can learn, along with the further lifting of Graphene addition, red phosphorus particle is covered by thick graphene layer,Therefore can only observe the exposed surface at composite of a small amount of red phosphorus particle.
For the element in further test compound material distributes, we have carried out element distribution to NRP/G20 sample and have surveyedExamination (elementmapping), correlated results as shown in Figure 2. Element distribution is carried out in the frame wire tag region of having chosen in Fig. 2 ATest (elementmapping). Find by test, this area distribution P element and C element, and this meets NRP/G20 sampleThe element composition of product, illustrates that red phosphorus and Graphene have occurred really compound.
In order further to characterize the microstructure between Graphene and red phosphorus, by transmission electron microscope (TEM) to implementingNanometer red phosphorus/graphene composite photocatalyst (NRP/G20) sample of example 2 is tested, and corresponding test result is as figureShown in 3A-Fig. 3 D. Fig. 3 A is the low power TEM shape appearance figure of NRP/G20 sample, can observe a large amount of flaky substances from Fig. 3 AExist, other material simultaneously in these flaky substance surface distributed. In order to observe the micro Distribution of NRP/G20 sampleStructure, selects local location in Fig. 3 A to amplify, and accordingly result as shown in Figure 3 B, can obviously be observed large from Fig. 3 BMeasure small red phosphorus uniform particles and be dispersed in the graphene-structured of sheet, formed loaded composite construction. Fig. 3 C isNRP/G20 sample is at the TEM shape appearance figure compared with under high-amplification-factor, and the particle diameter that can observe red phosphorus from this picture mainly dividesBelow cloth 100nm, only have a small amount of red phosphorus grain diameter between 100 to 200nm, this result can confirm reality of the present inventionThe red phosphorus particle of the Nano grade that the means of testing can be prepared. Fig. 3 D is that TEM pattern is amplified in the part of Fig. 3 C, can from this resultLearn, nanometer red phosphorus (NRP) can occur to contact closely with Graphene (graphene), and this may be due to Graphene tableHaving there is combination in the oxidation residual bond that face exists and the micro-oxide group on red phosphorus surface, thereby the two can be combined closely oneRise, form good electric transmission interface.
Fig. 4 is the XPS result of NRP/G20 sample, by the test of XPS, need to obtain the elemental composition information of this sampleAnd each list of elements surface chemistry status information. Fig. 4 A is the measurement result of NRP/G20 sample, from this figure, can learn thisSample is made up of P, C, tri-kinds of elements of O. Fig. 4 B is the XPS result of C1s, can learn that 284.5eV correspondence stone from this resultThe C-C key characteristic peak of China ink alkene, 286.6eV correspondence C-O peak, illustrates that Graphene is not reduced completely, and surface still exists oneFixed C-O residual bond. Fig. 4 C is the XPS result of P2p, and wherein 130.2eV correspondence the characteristic peak of NRP, and 134.5eV correspondence NRPThe oxide group characteristic peak on surface, shows that NRP surface exists certain oxidation residual bond. Fig. 4 D is the XPS result of O1s, to this knotFruit carries out can learning after swarming, the characteristic peak that goes out peak correspondence and O-C key at 532.5eV place, and 533.7eV place go out peak correspondencePositive PO4 3-Characteristic peak. Summing up above result can learn, in NRP/G20 sample, NRP and Graphene surface all exist oneFixed oxidation residual bond, and these oxidation residual bond distributions to nanometer red phosphorus, and two alternate combinations have certain contribution workWith.
Fig. 5 is the nitrogen adsorption desorption BET result of NRP, NRP/G10, NRP/G20, tetra-samples of NRP/G40. From four samples, in sample, there is not obvious meso-hole structure, and work as P/P in the nitrogen adsorption desorption isothermal curve shape of product0Exceed 0.9 withAfter, adsorbance (VolumeAdsorbed) numerical value of NRP, NRP/G10, NRP/G20, three samples now significantly rises, thisBecause the accumulation hole existing between red phosphorus nano particle causes. But for this sample of NRP/G40, in this regionThere is not obvious lifting in interior adsorbance (VolumeAdsorbed) numerical value, this result shows to improve when Graphene additionTo a certain extent, the space between NRP can be clogged, thereby not observe the existence of piling up hole, should in this result and Fig. 1 DThe SEM of sample shows that pattern is corresponding. In Fig. 5, inserted the reference area numerical value of 4 samples, contrasting these numerical value can send outExisting, the specific area of sample increases gradually along with the raising of Graphene addition, and this is mainly that Graphene has huge ratioSurface area causes, the interpolation of surperficial Graphene may provide side to the adsorption process in early stage in NRP/G composite photocatalyst processHelp.
In order to characterize the compound impact on NRP photocatalysis performance of Graphene, test RP, NRP, NRP/G10, NRP/G20, NRP/G30 (urge by nanometer red phosphorus/Graphene complex light that the addition that is embodiment 3 prepared Graphenes is 30wt%Agent) and the photo catalytic reduction aquatic products hydrogen performance of NRP/G40 sample under excited by visible light, the testing time of each sampleBe respectively 1 hour, reaction solution is triethanolamine solution, and corresponding test result as shown in Figure 6. From this result, can obtainKnow, commercial red phosphorus (RP) the Photocatalyzed Hydrogen Production efficiency of large particle diameter is minimum, and the hydrogen output of 1 hour is about 9 μ mol/g/h, and this is mainlyCommercial red phosphorus grain diameter is very large, and light-catalyzed reaction avtive spot is few, and simultaneously a large amount of light induced electrons and hole are sent out in mutually at its bodyGive birth to compound. Commercial red phosphorus nanometer beign preparation is become after nanometer red phosphorus (NRP), and its Photocatalyzed Hydrogen Production amount is brought up to 20 μ mol/g/H, more commercial RP is doubled, and this may be because the red phosphorus of Nano grade has more light-catalyzed reaction avtive spot,And dwindling of particle diameter reduced light induced electron from the material bodies distance that transmit on surface in opposite directions, thereby light induced electron and sky are reducedThere is re-compounded probability in cave. The interpolation of Graphene has material impact to the photocatalysis performance of NRP/G. When Graphene compoundWhen amount is 10wt%, the Photocatalyzed Hydrogen Production performance boost of NRP/G10 sample is to approximately 41 μ mol/g/h. When the compound quantity of GrapheneWhile continuing to bring up to 20wt%, its Photocatalyzed Hydrogen Production efficiency is further brought up to 65 μ mol/g/h. Afterwards, along with Graphene is compoundThe further raising of amount, its photocatalysis performance is fast-descending trend. In the time that the compound quantity of Graphene is brought up to 40wt%, light is urgedChange hydrogen output and taper to approximately 19 μ mol/g/h. Above result shows, in the time that the compound quantity of Graphene is less, to the photocatalysis of NRPPerformance has obvious facilitation. And the mechanism that causes this performance boost may be because Graphene has promoted NRP photoproduction electricityTransfer and the separative efficiency in son and hole, thus its photo catalytic reduction aquatic products hydrogen performance improved.
In order further to characterize nanometer, and the impact of the photocatalysis performance of graphene modified on red phosphorus, further surveyTry RP, NRP, NRP/G10, NRP/G20, NRP/G30 and NRP/G40 photocatalysis RhB dyestuff degradation property. Fig. 7 A isThe photocatalysis performance of the NRP sample of commercial red phosphorus (RP), nanometer red phosphorus (NRP) and Different adding amount graphene modified. SecretlyUnder state, stir after 30Min, can find that these samples exist obvious difference to the adsorption capacity of RhB. Commercial red phosphorus is to dyestuffAdsorption capacity the most weak, but by after commercial red phosphorus nanometer, on the adsorption capacity that can find NRP has occurred very significantlyRise, in 30Min, almost have 65% RhB to be adsorbed by it, this is mainly because the specific area of the more commercial red phosphorus of NRP has hadDue to significantly promoting. From after along with the raising of the interpolation of Graphene, the Dye Adsorption performance of NRP/G composite photo-catalyst occursSmall size lifting, but in the time that Graphene addition is brought up to 40wt%, this composite photo-catalyst adsorption capacity has occurred oneHop, within half an hour, the RhB of about 80wt% is absorbed. The explanation of above phenomenon, by red phosphorus nanometer or answer by GrapheneClose modification, all can improve its adsorption capacity to RhB. After 30Min upon adsorption, under visible illumination condition, test serial sampleThe photocatalytic degradation ability of product. From Fig. 7 A, can find, for commercial red phosphorus, can be right through this sample of illumination of 30MinApproximately 85% RhB realizes decolouring. But by after commercial red phosphorus nanometer, it is right that the NRP preparing can realize in 15MinThe decolouring completely of RhB, illustrates after nanometer, the light-catalyzed reaction avtive spot showed increased of NRP. Through the Graphene of different amountsAfter compound, there is obvious variation, NRP/G compared with NRP in the photocatalysis RhB degradation property of the NRP/G composite photo-catalyst obtaining10 can realize the decolouring completely to RhB in 10Min. When Graphene has added while bringing up to 20wt%, the light of NRP/G20Having there is obvious raising in catalysis RhB performance, just can realize the decolouring completely to RhB in about 3Min. Afterwards along with GrapheneThe further raising of addition, the photocatalysis RhB degradation property of NRP/G30 is got back to the level suitable with NRP, and works as GrapheneAddition is brought up to after 40wt%, and the photocatalysis RhB decoloration performance of NRP/G40 almost disappears. Above photocatalysis performance test chartBright, in the time that Graphene addition is less, can obviously improve the photocatalysis performance of composite photo-catalyst, this may be due to graphiteThe light induced electron that the interpolation of alkene has increased NRP separates and transfer ability, thereby has improved its photocatalysis RhB decoloration performance. ButWhen Graphene addition reaches after 4wt%, almost having there is disappearance in its photocatalysis RhB decoloration performance, causes the reason of this phenomenonBe because NRP/G40 is excessively strong to the adsorption capacity of RhB, in 30Min, almost adsorbed 80% RhB, when a large amount of RhB parcelsBehind NRP/G40 surface, will compete extinction process with its generation, photon is mainly caught by RhB, and NRP/G40 can not be excited,Thereby there is obvious reduction in the photocatalysis performance that makes NRP/G40. Because NRP/G20 has the strongest photocatalyticCan, we are by the photocatalysis circulation decolorization experiment to RhB, and absorption stability and the Photocatalytic Decoloration of investigating this sample are stableProperty, accordingly result is as shown in Figure 7 B. From this curve, can find, NRP/G20 is through 5 reaction cycle, still can beRealize the decolouring completely to RhB near 3Min, and its adsorption capacity is also stable, circulates its adsorption capacity also through 5 timesThere is not significantly decay. This phenomenon shows, RhB has very strong absorption stability and photocatalysis stability.
The above is only the preferred embodiment of the present invention, is noted that the ordinary skill people for the artMember, under the premise without departing from the principles of the invention, can also make some improvement, and these improvement should be considered as guarantor of the present inventionProtect scope.
Claims (4)
1. nanometer red phosphorus/graphene composite photocatalyst, is characterized in that: taking red phosphorus as base stock, pass through mechanical grindingMill method and ultrasonic flotation method are by red phosphorus nanometer, and the surface by nanometer red phosphorus particulate load to Graphene, makes nanometer red phosphorus/stoneChina ink alkene composite photo-catalyst.
2. nanometer red phosphorus/graphene composite photocatalyst according to claim 1, is characterized in that: described GrapheneAddition is 10wt%-40wt%.
3. nanometer red phosphorus/graphene composite photocatalyst according to claim 1, is characterized in that: described GrapheneAddition is 20wt%.
4. a preparation method for the nanometer red phosphorus/graphene composite photocatalyst described in any one in claim 1-3, its spyLevy and be to comprise the following steps:
(1) prepare nanoscale red phosphorus: prepare nanoscale red phosphorus by mechanical milling method and ultrasonic flotation method: by red 10g commercializationPhosphorus 400 DEG C of annealing 4 hours under nitrogen protection, then this red phosphorus is ground to 12h by 200r/Min in ball mill, red after grindingPhosphorus is ultrasonic dispersion in ethanol, centrifugal, removes the dry nanometer red phosphorus that obtains of upper strata suspension 80 degree;
(2) pass through Hunmer legal system for graphene oxide;
(3) take the prepared graphene oxide of step (2) according to proportioning, by super to load weighted graphene oxide and nanometer red phosphorusSound is dispersed in 60mL water, after disperseing completely, under xenon lamp, irradiates 2h, centrifugal, and washing is dry that nanometer red phosphorus/Graphene is compoundPhotochemical catalyst.
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