CN105435816A - CdxZn1-xS nanowire compound photocatalyst and preparing method and application thereof - Google Patents
CdxZn1-xS nanowire compound photocatalyst and preparing method and application thereof Download PDFInfo
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- CN105435816A CN105435816A CN201610046381.6A CN201610046381A CN105435816A CN 105435816 A CN105435816 A CN 105435816A CN 201610046381 A CN201610046381 A CN 201610046381A CN 105435816 A CN105435816 A CN 105435816A
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- 239000002070 nanowire Substances 0.000 title claims abstract description 94
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 21
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006104 solid solution Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 n-dodecyl Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention discloses a GQDs/CdxZn1-xS nanowire structure compound photocatalyst. The photocatalyst is formed by doping zinc ions in CdS nanowires to form solid solution CdxZn1-xS nanowires and attaching GQDs with good electron transport capability to the surfaces of the CdxZn1-xS nanowires, wherein the GQDs/CdxZn1-xS nanowire structure compound photocatalyst is of a linear structure. The GQDs/CdxZn1-xS nanowire scompound photocatalyst has the advantages that the prepared GQDs/CdxZn1-xS nanowire compound photocatalyst can efficiently catalyze paranitroaniline to prepare p-phenylenediamine under the irradiation of visible light, and is high in reaction speed and conversion rate and the like.
Description
Technical field
The invention belongs to the controlledly synthesis of nano material photochemical catalyst and environment and energy sustainable development field, be specifically related to a kind of GQDs/Cd
xzn
1-xthe preparations and applicatio of S nanowire composite photocatalyst prepares the method for p-phenylenediamine (PPD) in photo catalytic reduction paranitroanilinum.
Background technology
Photocatalysis is the crosspoint of photochemistry and catalytic science, generally refers to the photochemical reaction under catalyst participates in.In the face of the energy problem of growing tension and the environmental problem of form sternness, current most research work mainly concentrates on the environmental improvement such as degradation water and pollutants in air and improvement aspect, on the electrochemical process such as sun transformation of energy and Charge transfer on interface.Photocatalysis technology also may be used for organic chemical reactions.Recently, visible light catalytic has continued to obtain quantum jump in organic synthesis field, has become the research field of current hot topic.
Arylamine is important industrial chemicals and organic synthesis intermediate, is widely used in the industries such as medicine, agricultural chemicals, dyestuff, prepares mainly through corresponding reducing aromatic nitro compound method.In the middle of known various different method of reducing, the catalytic hydrogen reduction reaction of metal is the most effective.But this reaction needs to carry out under high Hydrogen Vapor Pressure and reaction temperature usually." light " is a kind of abundant, regenerative resource, and light-catalyzed reaction has the advantages such as reaction condition gentleness.
At present for visible light catalyst mainly some noble metal complexes, organic dyestuff and the plasma type metal of organic reaction.There are expensive, poor stability, needs and prepare the deficiencies such as specific catalyst size in these photochemical catalysts.Therefore, the inorganic base metal photochemical catalyst that the novel visible that exploitation is applicable to heterogeneous organic chemical reactions responds is particularly necessary.CdS is a kind of visible light catalyst, has been widely used in selective oxidation alcohols, photodissociation aquatic products hydrogen, reduction aromatic nitro to aromatic series amido.But still there is the deficiencies such as photo-generated carrier separative efficiency is low, superficial catalytic activation is weak in single CdS catalyst.One dimension Cd
xzn
1-xs nano wire is beneficial to transferring charge, has better catalytic activity than CdS.Will on the other hand, it is low that GQDs has bio-toxicity, is easy to load, can be used as the advantages such as electron acceptor.By GQDs and Cd
xzn
1-xs nano wire compound, then can obtain highly active composite photo-catalyst, but this composite is not also developed at present.The invention provides a kind of efficient GQDs/Cd
xzn
1-xthe preparation method of S nanowire composite photocatalyst.And this composite photo-catalyst can be applied to photo catalytic reduction paranitroanilinum prepares p-phenylenediamine (PPD), there is reaction speed fast, conversion ratio advantages of higher.
Summary of the invention
In view of the deficiencies in the prior art, the present invention is intended to provide the Cd with features such as catalytic efficiency is high, preparation cost is low, environmental friendliness
xzn
1-xs nanowire composite photocatalyst, its preparation method and its application.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of GQDs/Cd
xzn
1-xs nanometer wire structure composite photochemical catalyst, to be mixed in CdS nano wire by zinc ion and forms solid solution Cd
xzn
1-xs nano wire, and the GQDs with good electronics transmission capacity is attached to described Cd
xzn
1-xs nanowire surface is formed; Wherein, described GQD/Cd
xzn
1-xs nanowire composite photocatalyst has linear structure.
Based on above-mentioned GQDs/Cd
xzn
1-xs nanometer wire structure composite photochemical catalyst, the present invention also provides following preparation method.
One prepares GQDs/Cd
xzn
1-xthe method of S nanowire composite photocatalyst, said method comprising the steps of:
Step 1, under agitation, by 1mmolCd (Ac)
22H
2o and 2mmol DDTC is dissolved in 34mL ethylenediamine and 6mL n-dodecyl mereaptan mixed solvent and continuing magnetic force stirs 10 minutes;
Step 2, moves to the liquid rotating mixed in step (1) in 50mL teflon-lined reactor, reactor is placed in 180 DEG C of air dry oven reactions 48 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing by absolute ethyl alcohol and deionized water and obtain CdS nano wire powder three times, then gained CdS nano wire powder is placed in 60 DEG C of vacuum drying chambers dry 10 hours;
Step 3, takes the CdS of three parts of 0.0864g, 0.6mmol step (2) gained, mixes respectively from five nitric hydrate zinc of different amount, molar ratio is respectively: 1:0.5,1:1,1:2, join in 40mL ethylene glycol under agitation, stir 10 minutes, ultrasonic mixing;
Step 4, is transferred to the mixed liquor presoma in step (3) in 50mL reactor, is placed in 160 DEG C of air dry oven reactions 6 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing three times by absolute ethyl alcohol and deionized water, obtain the Cd of different Zn content
xzn
1-xs nano wire, then by gained Cd
xzn
1-xs nano wire is placed in 60 DEG C of vacuum drying chambers dry 8 hours;
Step 5, takes 0.20g pyrene and 20mL red fuming nitric acid (RFNA) is mixed in 50mL single necked round bottom flask, refluxes 12 hours under 80 DEG C of conditions, with absolute ethyl alcohol and deionized water alternately washing after products therefrom centrifugation, and drying 8 hours in 60 DEG C of vacuum drying chambers;
Step 6, under agitation, the powder weighing gained in 200 milligrams of steps (5) is placed in the NaOH solution of 40 milliliters of 0.2mol/L, proceeds in reactor after ultrasonic 2h, is placed in 200 DEG C of air dry oven reactions 10 hours.Question response to be cooled to gained liquid with the rotating speed of 10000r/min centrifugal 5 minutes after room temperature, gets supernatant and is frozen into solid postlyophilization and obtains GQDs in 24 hours;
Step 7, is made into the aqueous solution of 200mg/L by the GQDs obtained in step (6);
Step 8, gets quality for the Cd described in 80mg step (4)
xzn
1-xthe GQDs aqueous solution described in step (7) of S nano wire and different amount at room temperature mix and blend after 6 hours centrifugation obtain pressed powder, obtain GQDs/Cd
xzn
1-xs nanowire composite photocatalyst.
It should be noted that, in order to security consideration, shared by the liquid mixed in described step (2), volume is 80% of polytetrafluoroethylene (PTFE) reactor volume.
In order to obtain good CdxZn1-xS nano wire, as the preferred technical scheme of one, the molar ratio in described step (2) is 1:1.
Need to further illustrate, in described step (8), different amount GQDs is respectively 100 μ L, 200 μ L, 400 μ L.
As the preferred technical scheme of one, select GQDs and the GQDs/Cd of 200 μ L
xzn
1-xthe GQDs/Cd of S the fabricate of nanowires
xzn
1-xs composite photo-catalyst, tests to obtain this GQDs/Cd by elementary analysis
xzn
1-xin S nanowire composite photocatalyst, the amount of GQDs is 0.21% (wt).
The present invention also provides GQDs/Cd
xzn
1-xthe application of S nanowire composite photocatalyst, as described below:
One utilizes GQDs/Cd
xzn
1-xthe application of S nanowire composite photocatalyst in light-catalyzed reaction, described GQDs/Cd
xzn
1-xs nanowire composite photocatalyst is under the radiation of visible light of xenon lamp wavelength X >420nm, and logical nitrogen protection be photohole sacrifice agent with ammonium formate, photo catalytic reduction paranitroanilinum prepares p-phenylenediamine (PPD), and conversion ratio can reach more than 99%.
Beneficial effect of the present invention is: the GQDs/Cd of preparation
xzn
1-xs nanowire composite photocatalyst can prepare p-phenylenediamine (PPD) by efficient catalytic paranitroanilinum under visible light illumination, has reaction speed fast, conversion ratio advantages of higher.
Accompanying drawing explanation
Fig. 1 is CdS nano wire, Cd
xzn
1-xs nano wire and GQDs/Cd
xzn
1-xthe SEM picture (from left to right) of S nanowire composite photocatalyst.
Fig. 2 is GQDs/Cd
xzn
1-xthe TEM picture of S nanowire composite photocatalyst.
Fig. 3 is CdS, Cd
xzn
1-xs and GQDs/Cd
xzn
1-xthe XRD diffraction pattern of S nanowire composite photocatalyst.
Fig. 4 is CdS nano wire, Cd
xzn
1-xs nano wire and GQDs/Cd
xzn
1-xthe solid diffuse reflectance spectra of S nanowire composite photocatalyst.
Fig. 5 is CdS, Cd
xzn
1-xs, GQD/Cd
xzn
1-xthe fluorescence Spectra of S composite photo-catalyst pressed powder and the GQD aqueous solution.
Fig. 6 is GQDs/Cd
xzn
1-xs nanowire composite photocatalyst photo catalytic reduction paranitroanilinum prepares the ultraviolet absorption spectrum of p-phenylenediamine (PPD) reaction.
Fig. 7 is the Cd of different Zn, Cd ratio
xzn
1-xthe GQDs/Cd that S and different GQDs measures
xzn
1-xs nanowire composite photocatalyst photo catalytic reduction paranitroanilinum prepares the C/C of p-phenylenediamine (PPD) reaction
0variation diagram in time.
Fig. 8 is GQDs/Cd
xzn
1-xs composite photo-catalyst photo catalytic reduction paranitroanilinum in different dicyandiamide solutions prepares p-phenylenediamine (PPD) reaction C/C
0variation diagram in time.
Detailed description of the invention
Below with reference to accompanying drawing, the invention will be further described, it should be noted that, the present embodiment, premised on the technical program, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to the present embodiment.
The present invention is a kind of GQDs/Cd
xzn
1-xs nanometer wire structure composite photochemical catalyst, to be mixed in CdS nano wire by zinc ion and forms solid solution Cd
xzn
1-xs nano wire, and the GQDs with good electronics transmission capacity is attached to described Cd
xzn
1-xs nanowire surface is formed; Wherein, described GQD/Cd
xzn
1-xs nanowire composite photocatalyst has linear structure.
Based on above-mentioned GQDs/Cd
xzn
1-xs nanometer wire structure composite photochemical catalyst, the present invention also provides following preparation method.
One prepares GQDs/Cd
xzn
1-xthe method of S nanowire composite photocatalyst, said method comprising the steps of:
Step 1, under agitation, by 1mmolCd (Ac)
22H
2o and 2mmol DDTC is dissolved in 34mL ethylenediamine and 6mL n-dodecyl mereaptan mixed solvent and continuing magnetic force stirs 10 minutes;
Step 2, moves to the liquid rotating mixed in step (1) in 50mL teflon-lined reactor, reactor is placed in 180 DEG C of air dry oven reactions 48 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing by absolute ethyl alcohol and deionized water and obtain CdS nano wire powder three times, then gained CdS nano wire powder is placed in 60 DEG C of vacuum drying chambers dry 10 hours;
Step 3, takes the CdS of three parts of 0.0864g, 0.6mmol step (2) gained, mixes respectively from five nitric hydrate zinc of different amount, molar ratio is respectively: 1:0.5,1:1,1:2, join in 40mL ethylene glycol under agitation, stir 10 minutes, ultrasonic mixing;
Step 4, is transferred to the mixed liquor presoma in step (3) in 50mL reactor, is placed in 160 DEG C of air dry oven reactions 6 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing three times by absolute ethyl alcohol and deionized water, obtain the Cd of different Zn content
xzn
1-xs nano wire, then by gained Cd
xzn
1-xs nano wire is placed in 60 DEG C of vacuum drying chambers dry 8 hours;
Step 5, takes 0.20g pyrene and 20mL red fuming nitric acid (RFNA) is mixed in 50mL single necked round bottom flask, refluxes 12 hours under 80 DEG C of conditions, with absolute ethyl alcohol and deionized water alternately washing after products therefrom centrifugation, and drying 8 hours in 60 DEG C of vacuum drying chambers;
Step 6, under agitation, the powder weighing gained in 200 milligrams of steps (5) is placed in the NaOH solution of 40 milliliters of 0.2mol/L, proceeds in reactor after ultrasonic 2h, is placed in 200 DEG C of air dry oven reactions 10 hours.Question response to be cooled to gained liquid with the rotating speed of 10000r/min centrifugal 5 minutes after room temperature, gets supernatant and is frozen into solid postlyophilization and obtains GQDs in 24 hours;
Step 7, is made into the aqueous solution of 200mg/L by the GQDs obtained in step (6);
Step 8, gets quality for the Cd described in 80mg step (4)
xzn
1-xthe GQDs aqueous solution described in step (7) of S nano wire and different amount at room temperature mix and blend after 6 hours centrifugation obtain pressed powder, obtain GQDs/Cd
xzn
1-xs nanowire composite photocatalyst.
It should be noted that, in order to security consideration, shared by the liquid mixed in described step (2), volume is 80% of polytetrafluoroethylene (PTFE) reactor volume.
In order to obtain good CdxZn1-xS nano wire, as the preferred technical scheme of one, the molar ratio in described step (2) is 1:1.
Need to further illustrate, in described step (8), different amount GQDs is respectively 100 μ L, 200 μ L, 400 μ L.
As the preferred technical scheme of one, select GQDs and the GQDs/Cd of 200 μ L
xzn
1-xthe GQDs/Cd of S the fabricate of nanowires
xzn
1-xs composite photo-catalyst, tests to obtain this GQDs/Cd by elementary analysis
xzn
1-xin S nanowire composite photocatalyst, the amount of GQDs is 0.21% (wt).
The present invention also provides GQDs/Cd
xzn
1-xthe application of S nanowire composite photocatalyst, as described below:
One utilizes GQDs/Cd
xzn
1-xthe application of S nanowire composite photocatalyst in light-catalyzed reaction, described GQDs/Cd
xzn
1-xs nanowire composite photocatalyst is under the radiation of visible light of xenon lamp wavelength X >420nm, and logical nitrogen protection be photohole sacrifice agent with ammonium formate, photo catalytic reduction paranitroanilinum prepares p-phenylenediamine (PPD), and conversion ratio can reach more than 99%.
Embodiment one
Under agitation, by 1mmolCd (Ac)
22H
2o and 2mmol DDTC is dissolved in 34mL ethylenediamine and 6mL n-dodecyl mereaptan mixed solvent and continuing magnetic force stirs 10 minutes.This solution is transferred in 50mL teflon-lined reactor.Reactor is placed in 180 DEG C of air dry oven reactions 48 hours.Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, with the alternately washing of absolute ethyl alcohol and deionized water, dry CdS nano wire powder.Get 0.0864gCdS nano wire to mix with the five nitric hydrate zinc of 0.6mmol, join in 40mL ethylene glycol under agitation, stir 10 minutes, ultrasonic mixing.Then this mixed liquor is transferred in 50mL reactor, is placed in 160 DEG C of air dry oven reactions 6 hours.After reaction terminates, by product centrifugation, with the alternately washing of absolute ethyl alcohol and deionized water, dry Cd
xzn
1-xs nano wire.
Get 0.20g pyrene and 20mL red fuming nitric acid (RFNA) is mixed in 50mL single necked round bottom flask, reflux 12 hours under 80 DEG C of conditions, with absolute ethyl alcohol and deionized water alternately washing after products therefrom centrifugation, dry.Take the NaOH solution that 200 milligrams of step gained powder are placed in 40 milliliters of 0.2mol/L, proceed to after ultrasonic 2h in reactor, be placed in 200 DEG C of air dry oven reactions 10 hours.Question response to be cooled to gained liquid with the rotating speed of 10000r/min centrifugal 5 minutes after room temperature, gets supernatant and is frozen into solid postlyophilization and obtains GQDs in 24 hours.By the GQDs (200mg/L) of 200 μ L and the Cd of 80mg
xzn
1-xs nano wire at room temperature mix and blend after 6 hours centrifugation obtain pressed powder, obtain GQDs/Cd
xzn
1-xs nanowire composite photocatalyst.
Fig. 1 represents CdS nano wire, the Cd of preparation
xzn
1-xs nano wire and GQDs/Cd
xzn
1-xthe ESEM picture of S nano wire.As can be seen from Figure 1, product is nano thread structure, and length is about 10-15 μm.
As can be seen from TEM photo, Cd
xzn
1-xon S nano wire, load has GQDs, and size is less than 10nm (Fig. 2).
X-ray diffraction style shows, product is CdS, Cd
xzn
1-xs.GQDs/Cd
xzn
1-xs and Cd
xzn
1-xthe X-ray diffraction style of S is similar (Fig. 3).Elementary analysis shows GQDs/Cd
xzn
1-xin S, GQDs accounts for 0.21% (wt).
Doping of Zn ion and load GQDs are to Cd
xzn
1-xthe absorption of S nano wire to visible ray does not have much affect (Fig. 4).
After load GQDs, Cd
xzn
1-xthe fluorescent weakening (Fig. 5) of S nano wire, this result shows the separation of loaded favourable in photogenerated charge of GQDs.
Embodiment two
As application of the present invention:
The p-nitrophenyl amine aqueous solution of 30mL20mg/L is placed in beaker, adds 40mg ammonium formate under agitation, then take 20mgGQDs/Cd
xzn
1-xs composite photo-catalyst, makes catalyst be uniformly dispersed in reactant liquor in ultrasonic 3 minutes.Reactant liquor is gone out magnetic agitation 2 hours in dark, makes catalyst and reactant reach adsorption equilibrium.With the radiation of visible light of 500W xenon lamp wavelength (λ >420nm), the distance of light source and reaction system is 12cm.Every 2min sampling once, surveys the UV absorption of supernatant after centrifugation.Along with reaction is carried out, the color from yellow of solution gradually becomes colourless.
As shown in Figure 6, paranitroanilinum can be converted into p-phenylenediamine (PPD) completely in 6min.To 10min there is not reversible transition or decomposition, be converted into other product in product the further prolonging light time.
Embodiment three
Add the Cd of the CdS nano wire of the same quality of 20mg, different doping zinc concentration
xzn
1-xs nano wire and different loads amount GQDs/Cd
xzn
1-xs nano wire, photocatalysis experimental condition is consistent with embodiment two, studies the relative activity size of different sample.Result as shown in Figure 7, GQDs/Cd
xzn
1-xs nanowire composite is than single GQDs/Cd
xzn
1-xs all has better activity.When the amount of GQDs is when 0.21 (wt), the activity of composite catalyst is best.
Embodiment four
Join the p-nitrophenyl amine aqueous solution that three kinds of different solvents concentration are 20mg/L, it is 1:1, deionized water that three kinds of solvents are respectively absolute ethyl alcohol, absolute ethyl alcohol and deionized water volume ratio.The p-nitrophenyl amine aqueous solution getting 30mL different solvents respectively, in beaker, adds 40mg ammonium formate under agitation, then takes 20mgGQDs/Cd
xzn
1-xs nanowire composite photocatalyst, makes catalyst be uniformly dispersed in reactant liquor in ultrasonic 3 minutes.Reactant liquor is gone out magnetic agitation 2 hours in dark, makes catalyst and reactant reach adsorption equilibrium.With the radiation of visible light of 500W xenon lamp wavelength X >420nm, the distance of light source and reaction system is 12cm.Every 2min sampling once, surveys the UV absorption of supernatant after centrifugation.
Result of study as shown in Figure 8, GQDs/Cd
xzn
1-xthe catalytic activity of S nanowire composite photocatalyst in water is the highest.
For a person skilled in the art, according to above technical scheme and design, various corresponding change and distortion can be made, and all these change and distortion all should be included within the protection domain of the claims in the present invention.
Claims (6)
1. a GQDs/Cd
xzn
1-xs nanometer wire structure composite photochemical catalyst, is characterized in that, to be entrained in CdS nano wire and to form solid solution Cd by zinc ion
xzn
1-xs nano wire, and the GQDs with good electronics transmission capacity is attached to described Cd
xzn
1-xs nanowire surface is formed; Wherein, described GQD/Cd
xzn
1-xs nanowire composite photocatalyst has linear structure.
2. prepare GQDs/Cd as claimed in claim 1 for one kind
xzn
1-xthe method of S nanowire composite photocatalyst, is characterized in that, said method comprising the steps of:
Step 1, under agitation, by 1mmolCd (Ac)
22H
2o and 2mmol DDTC is dissolved in 34mL ethylenediamine and 6mL n-dodecyl mereaptan mixed solvent and continuing magnetic force stirs 10 minutes;
Step 2, moves to the liquid rotating mixed in step (1) in 50mL teflon-lined reactor, reactor is placed in 180 DEG C of air dry oven reactions 48 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing by absolute ethyl alcohol and deionized water and obtain CdS nano wire powder three times, then gained CdS nano wire powder is placed in 60 DEG C of vacuum drying chambers dry 10 hours;
Step 3, takes the CdS of three parts of 0.0864g, 0.6mmol step (2) gained, mixes respectively from five nitric hydrate zinc of different amount, molar ratio is respectively: 1:0.5,1:1,1:2, join in 40mL ethylene glycol under agitation, stir 10 minutes, ultrasonic mixing;
Step 4, is transferred to the mixed liquor presoma in step (3) in 50mL reactor, is placed in 160 DEG C of air dry oven reactions 6 hours; Treat that temperature is down to room temperature after reaction terminates, by product centrifugation, replace washing three times by absolute ethyl alcohol and deionized water, obtain the Cd of different Zn content
xzn
1-xs nano wire, then by gained Cd
xzn
1-xs nano wire is placed in 60 DEG C of vacuum drying chambers dry 8 hours;
Step 5, takes 0.20g pyrene and 20mL red fuming nitric acid (RFNA) is mixed in 50mL single necked round bottom flask, refluxes 12 hours under 80 DEG C of conditions, with absolute ethyl alcohol and deionized water alternately washing after products therefrom centrifugation, and drying 8 hours in 60 DEG C of vacuum drying chambers;
Step 6, under agitation, the powder weighing gained in 200 milligrams of steps (5) is placed in the NaOH solution of 40 milliliters of 0.2mol/L, proceeds in reactor after ultrasonic 2h, is placed in 200 DEG C of air dry oven reactions 10 hours.Question response to be cooled to gained liquid with the rotating speed of 10000r/min centrifugal 5 minutes after room temperature, gets supernatant and is frozen into solid postlyophilization and obtains GQDs in 24 hours;
Step 7, is made into the aqueous solution of 200mg/L by the GQDs obtained in step (6);
Step 8, gets quality for the Cd described in 80mg step (4)
xzn
1-xthe GQDs aqueous solution described in step (7) of S nano wire and different amount at room temperature mix and blend after 6 hours centrifugation obtain pressed powder, obtain GQDs/Cd
xzn
1-xs nanowire composite photocatalyst.
3. preparation GQDs/Cd according to claim 2
xzn
1-xthe method of S nanowire composite photocatalyst, is characterized in that, the molar ratio in described step (3) is 1:1.
4. preparation GQDs/Cd according to claim 2
xzn
1-xthe method of S nanowire composite photocatalyst, is characterized in that, in described step (8), different amount GQDs is respectively 100 μ L, 200 μ L, 400 μ L.
5. preparation GQDs/Cd according to claim 4
xzn
1-xthe method of S nanowire composite photocatalyst, is characterized in that, selects GQDs and the GQDs/Cd of 200 μ L
xzn
1-xthe GQDs/Cd of S the fabricate of nanowires
xzn
1-xs composite photo-catalyst, tests to obtain this GQDs/Cd by elementary analysis
xzn
1-xin S nanowire composite photocatalyst, the amount of GQDs is 0.21% (wt).
6. one kind utilizes GQDs/Cd as claimed in claim 1
xzn
1-xthe application of S nanowire composite photocatalyst in light-catalyzed reaction, is characterized in that, described GQDs/Cd
xzn
1-xs nanowire composite photocatalyst is under the radiation of visible light of xenon lamp wavelength X >420nm, and logical nitrogen protection be photohole sacrifice agent with ammonium formate, photo catalytic reduction paranitroanilinum prepares p-phenylenediamine (PPD), and conversion ratio can reach more than 99%.
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| CN107876094A (en) * | 2017-11-07 | 2018-04-06 | 常州大学 | Three dish alkene polymer NTP/ zinc-cadmium sulfides Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalysts |
| CN108993614A (en) * | 2018-04-16 | 2018-12-14 | 温州大学 | A kind of preparation method of the CdS photochemical catalyst of flower ball-shaped zinc ion doping |
| CN109225263A (en) * | 2018-07-27 | 2019-01-18 | 广东工业大学 | A kind of CdS/TiO2Nano heterojunction photocatalysis material and its preparation method and application |
| CN111203255A (en) * | 2020-01-16 | 2020-05-29 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876094A (en) * | 2017-11-07 | 2018-04-06 | 常州大学 | Three dish alkene polymer NTP/ zinc-cadmium sulfides Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalysts |
| CN108993614A (en) * | 2018-04-16 | 2018-12-14 | 温州大学 | A kind of preparation method of the CdS photochemical catalyst of flower ball-shaped zinc ion doping |
| CN108993614B (en) * | 2018-04-16 | 2021-03-16 | 温州大学 | Preparation method of ball-flower-shaped zinc ion doped CdS photocatalyst |
| CN109225263A (en) * | 2018-07-27 | 2019-01-18 | 广东工业大学 | A kind of CdS/TiO2Nano heterojunction photocatalysis material and its preparation method and application |
| CN111203255A (en) * | 2020-01-16 | 2020-05-29 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
| CN111203255B (en) * | 2020-01-16 | 2021-05-28 | 西安交通大学 | N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst |
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