CN106238085A - A kind of oxygen doping nitrogen carbide noble metal composite photo-catalyst, preparation method and application - Google Patents
A kind of oxygen doping nitrogen carbide noble metal composite photo-catalyst, preparation method and application Download PDFInfo
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- CN106238085A CN106238085A CN201610605543.5A CN201610605543A CN106238085A CN 106238085 A CN106238085 A CN 106238085A CN 201610605543 A CN201610605543 A CN 201610605543A CN 106238085 A CN106238085 A CN 106238085A
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- nitrogen carbide
- oxygen doping
- noble metal
- doping nitrogen
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 458
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 229
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000001301 oxygen Substances 0.000 title claims abstract description 141
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 141
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000002905 metal composite material Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims description 83
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 20
- 238000007146 photocatalysis Methods 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 238000007540 photo-reduction reaction Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000006471 dimerization reaction Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940071536 silver acetate Drugs 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000001629 suppression Effects 0.000 abstract description 4
- 239000002082 metal nanoparticle Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 238000005406 washing Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 238000006392 deoxygenation reaction Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000000703 high-speed centrifugation Methods 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005304 joining Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 5
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 4
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- -1 halo ion Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/394—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a kind of oxygen doping nitrogen carbide noble metal composite photo-catalyst, preparation method and application, hydrogen peroxide is utilized to prepare oxygen doping nitrogen carbide, noble metal nano particles can be uniformly dispersed in the surface of oxygen doping nitrogen carbide, has good contact surface and load effect；The catalyst of preparation has good catalytic effect to nitroaromatic；Compared with prior art, compound by oxygen doping nitrogen carbide and noble metal of the present invention, form visible light-responded composite catalyst, this complex can improve the absorption region to visible ray, accelerate being combined of electron transfer rate, suppression light induced electron and hole, to be greatly improved the photocatalytic activity of oxygen doping nitrogen carbide, degraded and industrialization for its organic pollution in being applied to organic catalysis, environment provide possible.
Description
Technical field
The invention belongs to the preparation field of composite, be specifically related to a kind of oxygen doping nitrogen carbide-noble metal complex light and urge
Agent, preparation method and application.
Background technology
Since Liu and Cohen (Science, 1989,245,841 842) of University of California in 1989 proposes theoretically
Since nitrogen carbide covalent crystal, carboritride because the aspect such as optics, mechanics have excellence performance and by various countries' science
The concern of family.Wherein class graphite phase carbon nitride is most stable of phase under room temperature, has nontoxic and visible light-responded (quasiconductor band gap
The character such as 2.7eV) so that it is there is the most wide application prospect at catalytic field.Graphite-phase nitrogen carbide is high with its photocatalytic activity,
Good stability, cost of material cheaply, especially do not contain this outstanding advantages of metal, make it a kind of novel photocatalyst,
There is great research and using value.
But, substantial amounts of research shows, unmodified graphite-phase nitrogen carbide exists that photocatalytic activity is the highest, degradation efficiency is low
Etc. shortcoming so that it is application is seriously restricted.And graphite-phase nitrogen carbide is modified, can be by most inorganic compound
With inorganic metal ion can in conjunction with or be inserted in graphite-phase nitrogen carbide substrate, expanded the response range of its visible ray,
The light induced electron of suppression graphite-phase nitrogen carbide and being combined of hole, improve the photocatalytic activity of graphite-phase nitrogen carbide.
And this significantly more efficient ameliorative way of semiconductors coupling also result in chemist and the extensive concern of material scholar.
Such as, Wang Xinchen professor seminar (ChemSusChem, 2013,7,738 742) of University of Fuzhou uses ferrocene to graphite-phase
Nitrogen carbide is modified, and benzene oxidatoin under visible light illumination, directly can be produced phenol by the graphite-phase nitrogen carbide after modification.
Additionally, graphite-phase nitrogen carbide also has been carried out modifying (Adv.Mater., 2014,26,805 809) by they with iodine, obtained
Composite shows the catalysis activity being better than graphite-phase nitrogen carbide on photocatalysis hydrogen production.The Cheng Huiming professor of the Chinese Academy of Sciences
Seminar (J.Am.Chem.Soc., 2010,132,11,642 11648) has carried out modification with sulfur to graphite-phase nitrogen carbide, it is thus achieved that
The sulfur doping graphite-phase nitrogen carbide composite photocatalyst hydrogen manufacturing material of high catalytic activity.Chinese patent (CN102931418A) is announced
One utilizes the silicon dioxide for hard template, prepares mesoporous nitrogen-doped carbon material by nanometer casting method, then utilizes halogenated hydrocarbons
Being alkylated reaction makes nitrogen-doped carbon material surface quaternized, the mode exchanged by ion make the moon with noble metal from
Subbase group replaces halo ion, is bundled in material surface, finally utilizes reducing agent reduction precious metal ion, prepares mesoporous
Nitrogen carbide supported precious metal nano-particle, and have studied its application on cathodic oxygen reduction, show the electrocatalysis of excellence
Energy.Program preparation process uses in complicated hard template method, and application also mainly for hydrogen reduction.
In sum, use the modification of graphite-phase nitrogen carbide or doping, can effectively improve graphite-phase nitrogen carbide to can
See absorption and the utilization of light, improve catalysis activity and selectivity.But, the research master of the nitrogen carbide composite photo-catalyst that adulterates at present
Photochemistry to be concentrated on produces hydrogen and degradation of organic dyes field, and for nitroaromatic reducing catalyst exploitation still
Blank.
Summary of the invention
It is an object of the invention to provide a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst and preparation method thereof,
Utilizing hydrogen peroxide to prepare oxygen doping nitrogen carbide, noble metal nano particles can be uniformly dispersed in the surface of oxygen doping nitrogen carbide, has
Well contact surface and load effect.
Present invention also offers the purposes of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, to nitro aromatic
Compound has good catalytic effect.
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst that the present invention provides, including following step
Rapid:
(1) nitrogen carbide is prepared；
(2) oxygen doping nitrogen carbide is prepared；
(3) oxygen doping nitrogen carbide-noble metal composite-material is prepared.
After step (1) is particularly as follows: calcine carbon nitrogen source, obtain nitrogen carbide, the suspension of preparation nitrogen carbide；
Step (2) is particularly as follows: the suspension of nitrogen carbide step (1) prepared mixes with hydrogen peroxide, after hydro-thermal reaction,
Cool down, separate, wash, be dried, obtain oxygen doping nitrogen carbide, prepare the suspension of oxygen doping nitrogen carbide；
Step (3), particularly as follows: mixed with precious metal salt solution by the suspension of the oxygen doping nitrogen carbide obtained, stirs 5-50
Hour, then photo-reduction noble metal, centrifugation, washed product, i.e. obtain oxygen doping nitrogen carbide-noble metal composite photo-catalyst
Material.
Further, in step (1) carbon nitrogen source in tripolycyanamide, cyanamid dimerization or carbamide one or more.
Further, calcining described in step (1) is particularly as follows: calcine 48 hours at 450 650 DEG C；
Further, after step (1) obtains nitrogen carbide, produce and grind, obtain powder, then be placed in ultrasonic disperse in alcoholic solvent,
Obtain the suspension of nitrogen carbide；
Alcoholic solvent described in step (1) is selected from methanol, ethanol, normal propyl alcohol, isopropanol, butanol, ethylene glycol, 1,2-the third two
One or more in alcohol, 1,3-propylene glycol or glycerol.
Further, in step (1), the ultrasonic disperse time is 3 10 hours；The concentration of the suspension of described nitrogen carbide is
0.1–3mg/mL。
In step (2), the suspension of nitrogen carbide and the volume ratio of hydrogen peroxide are 0.1 3:1；The mass concentration of hydrogen peroxide is
10-30%；Described hydrothermal reaction condition is: hydro-thermal reaction 3 15 hours at 100 180 DEG C；Described it is separated into centrifugation, institute
State washing for using deionized water, washing with alcohol product 3-5 time successively；
Further, it is dried particularly as follows: the oxygen doping nitrogen carbide obtained is put into vacuum drying oven described in step (2)
In at 50 80 DEG C, be dried under vacuum to constant weight；
Further, step (2) also includes: by dried oxygen doping nitrogen carbide ultrasonic disperse in water, is formed and suspends
Liquid；The concentration of the suspension of gained oxygen doping nitrogen carbide is 0.1 10mg/mL；
One or more in gold chloride, sodium chloraurate, silver nitrate, silver acetate of slaine described in step (3), its
In middle oxygen doping nitrogen carbide suspension, the quality of oxygen doping nitrogen carbide is 1 with the mass ratio of the noble metal in precious metal salt solution:
0.0001–0.2；
Photo-reduction noble metal described in step (3) is particularly as follows: by mixed liquor irradiation 35 hours, Qi Zhongzi under uviol lamp
The power of outer lamp is more than or equal to 50W；
Described washed product, particularly as follows: obtained product is used deionized water, washing with alcohol product 3-5 time successively, to obtain final product
To oxygen doping nitrogen carbide-noble metal composite photo-catalyst；
A kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst that the present invention provides, uses above method to prepare.
The application of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst that the present invention provides, particularly as follows: to nitro virtue
The photo catalytic reduction of aroma compounds.
Concrete application process is: oxygen doping nitrogen carbide-noble metal composite photo-catalyst is joined nitroaromatic
In solution, and add sacrifice agent, ultrasonic disperse 3-5 hour, obtain suspension, then pass to nitrogen deoxygenation, then simulated solar irradiation spoke
According to, photo catalytic reduction nitroaromatic.
Described oxygen doping nitrogen carbide-noble metal composite photo-catalyst, nitroaromatic, the mass ratio of sacrifice agent
For: oxygen doping nitrogen carbide-noble metal composite photo-catalyst: nitroaromatic: sacrifice agent=1:0.001-1:0.5-5；Mould
The time intending sunlight irradiation is 0.5-3 hour；Described nitroaromatic be respectively paranitrophenol, metanitrophenol,
Onitrophenol, paranitroanilinum, Nitrobenzol, paranitroanisole, parachloronitrobenzene, p-Nitrobromobenzene.
The carbon source in the present invention being first and nitrogen source are not limited to a certain kind, but the most several mixed forms, this
Sample is conducive to obtaining the nitrogen carbide with structural specificity, lays the foundation for follow-up modification and modification；Secondly, mix at acquisition oxygen
During miscellaneous nitrogen carbide, the oxygen adulterated comes from hydrogen peroxide, its after high-temperature heat treatment waste liquid to environment friendly and pollution-free or secondary is dirty
Contaminate the lowest, and the dispersibility of the oxygen doping nitrogen carbide obtained is improved significantly, provides prerequisite for follow-up carried noble metal
Condition；Finally, when obtaining oxygen doping nitrogen carbide-noble metal composite-material, the just ultraviolet light of employing, relative to visible ray,
In hgher efficiency, be conducive to area load noble metal granule pattern, size and the control of distribution, it might even be possible to obtain single former
Sub-rank or the noble metal granule of nanocluster rank.Additionally, prepared oxygen doping nitrogen carbide-noble metal composite-material conduct
Visible light catalyst, nitroaromatic carries out amination provides a kind of simple, green path for transformation.
Compared with prior art, one aspect of the present invention, utilize oxygen element that nitrogen carbide is modified, it is thus achieved that oxygen doping carbonization
Nitrogen semi-conductor material, improves its absorption to visible ray；On the other hand, utilize noble metal to have the advantage of relatively low work function,
Play electronics excellence conductor, can be with on fast transfer electronics to substrate, it is achieved hydrogenation hydrogenation process；It is crucial that, at light also
Under former effect, the present invention can obtain atomic level or the noble metal granule of nanocluster rank, can imitate at plasma
Under the effect answered, can be effectively improved electronics transmission efficiency and can fabulous suppression light induced electron and hole compound, significantly
Improve and improve photocatalysis efficiency.Compound by oxygen doping nitrogen carbide and noble metal of the present invention, forms visible light-responded answering
Closing catalyst, this complex can improve the absorption region to visible ray, accelerate electron transfer rate, suppression light induced electron and sky
Being combined of cave, will be greatly improved the photocatalytic activity of oxygen doping nitrogen carbide, for it in being applied to organic catalysis, environment
The degraded of organic pollution and industrialization provide may.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of embodiment 1 resulting materials；
Fig. 2 is scanning electron microscope (SEM) photo of embodiment 2 resulting materials；
Fig. 3 is scanning electron microscope (SEM) photo of embodiment 3 resulting materials；
Fig. 4 is the catalytic conversion figure of embodiment 1-9 resulting materials.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to following
Case.
Embodiment 1
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 10 grams of tripolycyanamide and be placed in Muffle furnace, at 600 DEG C
Calcine 5 hours, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow, then take 200 milligrams of carbonizations
Nitrogen pressed powder ultrasonic disperse is in 200 ml methanol solvents, and the nitrogen carbide suspension i.e. obtaining 1 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 100 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 200 milliliters of mass fractions are 20% is sufficiently stirred for, hydro-thermal reaction 6 hours at 120 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 60 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 1 milligram/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-metal/composite material: take 40 milliliters of oxygen doping nitrogen carbide suspensions, add 10
Milliliter concentration is the chlorauric acid solution of 0.001 mol/L, is stirred at room temperature 12 hours, places it in irradiation 5 under uviol lamp little
Time, centrifugation, use deionized water, washing with alcohol product 3-5 time successively, i.e. obtain oxygen doping nitrogen carbide-gold composite photocatalyst
Agent material, its electron scanning micrograph is as shown in Figure 1.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
The catalytic applications of oxygen doping nitrogen carbide-gold composite photo-catalyst: take 20 milligrams of oxygen doping nitrogen carbide-gold complex light and urge
Agent material joins in the p-nitrophenyl phenol solution that 40 milliliters of concentration is 20 mg/litre, and ultrasonic disperse was suspended after 3 hours
Liquid, after adding 20 milligrams of sacrifice agent ammonium formates, then is passed through nitrogen deoxygenation in suspension and as protection gas, puts into simulation
Irradiation (with the 300W xenon lamp more than 420 nm filter, Beijing Bo Feilai Science and Technology Ltd.) under sunlight, every necessarily
Time takes a sample, tests this material photo-reduction performance to paranitrophenol, and after 0.5 hour, the conversion ratio of paranitrophenol is about
It is 99.9%, as shown in Figure 4.
Embodiment 2
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 15 grams of cyanamid dimerizations and be placed in Muffle furnace, at 650 DEG C
Calcine 8 hours, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow, then take 100 milligrams of carbonizations
Nitrogen pressed powder ultrasonic disperse is in 200 milliliters of alcohol solvents, and the nitrogen carbide suspension i.e. obtaining 0.5 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 100 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 80 milliliters of mass fractions are 30% is sufficiently stirred for, hydro-thermal reaction 4 hours at 180 DEG C, natural
Being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum to perseverance at 50 DEG C
Weight, i.e. can get oxygen doping nitrogen carbide, weighs 40 milligrams of oxygen doping nitrogen carbide ultrasonic disperse and be configured to 2 mg/ml in water
Suspension stand-by；
(3) preparation of oxygen doping nitrogen carbide-silver composite material: take 20 milliliters of oxygen doping nitrogen carbide suspensions, add 25
Milliliter concentration is the silver nitrate solution of 0.001 mol/L, is stirred at room temperature 15 hours, places it in irradiation 4 under uviol lamp little
Time, centrifugation, use deionized water, washing with alcohol product 3-5 time successively, i.e. obtain oxygen doping nitrogen carbide-silver composite photocatalyst
Agent material, its electron scanning micrograph is as shown in Figure 2.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 20 milligrams of oxygen doping nitrogen carbide-gold photocatalysis composites and joining 40 milliliters of concentration is 20 mg/litre
In m-nitro phenol solution, ultrasonic disperse obtains suspension after 3 hours, after adding 20 milligrams of sacrifice agent ammonium oxalate, then to suspension
Liquid is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with more than 420 nm filter
300W xenon lamp, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material to metanitrophenol
Photo-reduction performance, after 0.5 hour, the conversion ratio of metanitrophenol is about 98%, as shown in Figure 4.
Embodiment 3
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 20 grams of carbamide and be placed in Muffle furnace, calcines 8 at 550 DEG C
Hour, it is cooled to room temperature, after being fully ground, i.e. obtains the nitrogen carbide pressed powder of yellow, then take 300 milligrams of nitrogen carbide solid
Body powder ultrasonic is scattered in 100 milliliters of normal propyl alcohol solvents, and the nitrogen carbide suspension i.e. obtaining 3 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 50 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 100 milliliters of mass fractions are 15% is sufficiently stirred for, hydro-thermal reaction 8 hours at 160 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 120 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 6 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-Doré metal composite: take 10 milliliters of oxygen doping nitrogen carbide dispersion liquids,
Form suspension, add sodium chloraurate solution that 5 milliliters of concentration is 0.001 mol/L and 5 milliliters of concentration be 0.001 mole/
The silver acetate solution risen, is stirred at room temperature 20 hours, places it in irradiation 4 hours, centrifugation under uviol lamp, spend successively
Ionized water, washing with alcohol product 3-5 time, i.e. obtain oxygen doping nitrogen carbide-Doré metal photocatalysis composite.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 20 milligrams of oxygen doping nitrogen carbide-Doré metal photocatalysis composites and joining 40 milliliters of concentration is 25 millis
In the ortho-nitrophenyl phenol solution of grams per liter, ultrasonic disperse obtains suspension after 3 hours, after adding 30 milligrams of sacrifice agent ammonium formates, then
In suspension, it is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with more than 420 nanometer filters
The 300W xenon lamp of mating plate, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material to adjacent nitre
The photo-reduction performance of base phenol, after 3 hours, the conversion ratio of onitrophenol is about 96%, as shown in Figure 4.
Embodiment 4
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 5 grams of tripolycyanamide and 5 grams of cyanamid dimerizations are placed in Muffle furnace
In, calcine 5 hours at 550 DEG C, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow, then
Taking 200 milligrams of nitrogen carbide pressed powder ultrasonic disperse in 100 milliliters of isopropanol solvents, the nitrogen carbide obtaining 2 mg/ml is hanged
Supernatant liquid is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 100 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 50 milliliters of mass fractions are 30% is sufficiently stirred for, hydro-thermal reaction 15 hours at 120 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 100 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 4 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-metal/composite material: take 10 milliliters of oxygen doping nitrogen carbide dispersion liquids, is formed and suspends
Liquid, adds chlorauric acid solution that 4 milliliters of concentration is 0.001 mol/L and gold chloride that 6 milliliters of concentration is 0.001 mol/L
Sodium solution, is stirred at room temperature 12 hours, places it in irradiation 3 under uviol lamp little constantly, and deionization is used in centrifugation successively
Water, washing with alcohol product 3-5 time, i.e. obtain oxygen doping nitrogen carbide-gold photocatalysis composite.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 20 milligrams of oxygen doping nitrogen carbide-gold photocatalysis composites and joining 40 milliliters of concentration is 10 mg/litre
In p-nitrophenyl amine aqueous solution, ultrasonic disperse obtains suspension after 3 hours, after adding 15 milligrams of sacrifice agent ammonium formates, then to suspension
Liquid is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with more than 420 nm filter
300W xenon lamp, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material to paranitroanilinum
Photo-reduction performance, after 2 hours, the conversion ratio of paranitroanilinum is about 85%, as shown in Figure 4.
Embodiment 5
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 5 grams of tripolycyanamide and 15 grams of cyanamid dimerizations are placed in Muffle furnace
In, calcine 5 hours at 550 DEG C, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow, then
Taking 200 milligrams of nitrogen carbide pressed powder ultrasonic disperse in 100 milliliters of isopropanol solvents, the nitrogen carbide obtaining 2 mg/ml is hanged
Supernatant liquid is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 100 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 50 milliliters of mass fractions are 28% is sufficiently stirred for, hydro-thermal reaction 15 hours at 120 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 100 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 4 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-metal/composite material: take 10 milliliters of oxygen doping nitrogen carbide dispersion liquids, is formed and suspends
Liquid, adds chlorauric acid solution that 4 milliliters of concentration is 0.001 mol/L and gold chloride that 6 milliliters of concentration is 0.001 mol/L
Sodium solution, is stirred at room temperature 10 hours, places it in irradiation 3 hours under uviol lamp, centrifugation, successively with deionized water,
Washing with alcohol product 3-5 time, i.e. obtains oxygen doping nitrogen carbide-gold photocatalysis composite.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 20 milligrams of oxygen doping nitrogen carbide-gold photocatalysis composites and joining 40 milliliters of concentration is 10 mg/litre
In nitrobenzene solution, ultrasonic disperse obtains suspension after 3 hours, after adding 25 milligrams of sacrifice agent ammonium oxalate, then in suspension
It is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with the 300W more than 420 nm filter
Xenon lamp, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test the photo-reduction of this material p-nitrophenyl
Performance, after 1 hour, the conversion ratio of Nitrobenzol is about 75%, as shown in Figure 4.
Embodiment 6
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 4.5 grams of tripolycyanamide and 5.5 grams of cyanamid dimerizations are placed in horse
Not in stove, calcine 6 hours at 560 DEG C, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow,
Then take 200 milligrams of nitrogen carbide pressed powder ultrasonic disperse in 100 milliliters of ethylene glycol solvents, obtain the carbonization of 2 mg/ml
Nitrogen suspension is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 80 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 40 milliliters of mass fractions are 25% is sufficiently stirred for, hydro-thermal reaction 10 hours at 130 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 60 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 3 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-metal/composite material: take 10 milliliters of oxygen doping nitrogen carbide dispersion liquids, is formed and suspends
Liquid, adds chlorauric acid solution that 0.4 milliliter of concentration is 0.001 mol/L and chlorine that 0.6 milliliter of concentration is 0.001 mol/L
Sodium aurate solution, is stirred at room temperature 15 hours, places it in irradiation 3 under uviol lamp little constantly, centrifugation, spend successively from
Sub-water, washing with alcohol product 3-5 time, i.e. obtain oxygen doping nitrogen carbide-gold photocatalysis composite.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 15 milligrams of oxygen doping nitrogen carbide-gold photocatalysis composites and joining 40 milliliters of concentration is 10 mg/litre
In p-nitrophenyl phenol solution, ultrasonic disperse obtains suspension after 3 hours, adds 10 milligrams of sacrifice agent ammonium formates and 10mg ammonium oxalate
After, then in suspension, it is passed through nitrogen deoxygenation and as protection gas, put into irradiation under simulated solar irradiation (with more than 420
The 300W xenon lamp of nm filter, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material
Photo-reduction performance to paranitroanilinum, after 0.5 hour, the conversion ratio of paranitrophenol is about 98%, as shown in Figure 4.
Embodiment 7
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: the carbamide weighing 15 grams of tripolycyanamide and 10 grams is placed in Muffle furnace
In, calcine 6 hours at 500 DEG C, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide pressed powder of yellow, then
Take 100 milligrams of nitrogen carbide pressed powder ultrasonic disperse mixing in 100 ml methanol, 100 milliliters of isopropanols and 50 milliliters of glycerol
In bonding solvent, the nitrogen carbide suspension i.e. obtaining 0.4 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 150 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 75 milliliters of mass fractions are 30% is sufficiently stirred for, hydro-thermal reaction 10 hours at 140 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 50 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 1 milligram/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-silver composite material: take 30 milliliters of oxygen doping nitrogen carbide suspensions, add 10
Milliliter concentration is the silver acetate solution of 0.001 mol/L, is stirred at room temperature 10 hours, places it in irradiation 3 under uviol lamp little
Time, centrifugation, use deionized water, washing with alcohol product 3-5 time successively, i.e. obtain oxygen doping nitrogen carbide-silver composite photocatalyst
Agent material.
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 15 milligrams of oxygen doping nitrogen carbide-gold photocatalysis composites and joining 40 milliliters of concentration is 10 mg/litre
To in paranitroanisole solution, ultrasonic disperse obtains suspension after 3 hours, adds 15 milligrams of sacrifice agent ammonium acetates, then to outstanding
Supernatant liquid is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with more than 420 nm filter
300W xenon lamp, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material to p-nitrophenyl
The photo-reduction performance of methyl ether, after 1.5 hours, the conversion ratio of paranitroanisole is about 86%, as shown in Figure 4.
Embodiment 8
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: the mixture weighing 10 grams of cyanamid dimerizations and 10 grams of carbamide is placed in
In Muffle furnace, calcine 5 hours at 650 DEG C, be cooled to room temperature, after being fully ground, i.e. obtain the nitrogen carbide solid powder of yellow
End, then takes 300 milligrams of nitrogen carbide pressed powder ultrasonic disperse in 70 milliliters of 1,3-PDs and the mixing of 30 milliliters of isopropanols
In solvent, the nitrogen carbide suspension i.e. obtaining 3 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 50 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 100 milliliters of mass fractions are 15% is sufficiently stirred for, hydro-thermal reaction 8 hours at 160 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 120 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 6 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-Doré metal composite: take 10 milliliters of oxygen doping nitrogen carbide dispersion liquids,
Form suspension, add sodium chloraurate solution that 18 milliliters of concentration is 0.001 mol/L and 2 milliliters of concentration is 0.001 to rub
You/liter silver nitrate solution, be stirred at room temperature 30 hours, place it in irradiation 4 hours under uviol lamp, centrifugation, successively
With deionized water, washing with alcohol product 3-5 time, i.e. obtain oxygen doping nitrogen carbide-Doré metal photocatalysis composite；
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 10 milligrams of oxygen doping nitrogen carbide-Doré metal photocatalysis composites and joining 40 milliliters of concentration is 5 millis
In the parachloronitrobenzene solution of grams per liter, ultrasonic disperse obtains suspension after 3 hours, after adding 8 milligrams of sacrifice agent ammonium formates, then
In suspension, it is passed through nitrogen deoxygenation and as protection gas, puts into irradiation under simulated solar irradiation (with more than 420 nanometer filters
The 300W xenon lamp of mating plate, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, test this material to chlorine
The photo-reduction performance of Nitrobenzol, after 3 hours, the conversion ratio of parachloronitrobenzene is about 65%, as shown in Figure 4.
Embodiment 9
The preparation method of a kind of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, comprises the following steps:
(1) synthesis of nitrogen carbide and the preparation of suspension: weigh 10 grams of tripolycyanamide, 10 grams of cyanamid dimerizations and 10 grams of carbamide
Mixture be placed in Muffle furnace, at 650 DEG C calcine 4 hours, be cooled to room temperature, after being fully ground, i.e. obtain the carbon of yellow
Change nitrogen pressed powder, then take 300 milligrams of nitrogen carbide pressed powder ultrasonic disperse in containing 50 milliliters of ethanol, 50 milliliter 1,2-third
Glycol, 100 milliliters of isopropanols mixed solvent in, the nitrogen carbide suspension i.e. obtaining 1.5 mg/ml is stand-by；
(2) synthesis of oxygen doping nitrogen carbide and the preparation of suspension: the suspension taking 50 milliliters of above-mentioned nitrogen carbide is put into instead
Answer in still, add after the hydrogen peroxide that 100 milliliters of mass fractions are 10% is sufficiently stirred for, hydro-thermal reaction 8 hours at 100 DEG C, from
So being cooled to room temperature, high speed centrifugation separates, and uses deionized water, washing with alcohol product 3-5 time successively, is dried under vacuum at 50 DEG C
Constant weight, i.e. can get oxygen doping nitrogen carbide, weigh 60 milligrams of oxygen doping nitrogen carbide ultrasonic disperse be configured in water 2 milligrams/in the least
The suspension risen is stand-by；
(3) preparation of oxygen doping nitrogen carbide-Doré metal composite: take 20 milliliters of oxygen doping nitrogen carbide dispersion liquids,
Form suspension, add sodium chloraurate solution that 5 milliliters of concentration is 0.001 mol/L and 15 milliliters of concentration is 0.001 to rub
You/liter silver acetate solution, be stirred at room temperature 40 hours, place it in irradiation 4 hours under uviol lamp, centrifugation, successively
With deionized water, washing with alcohol product 3-5 time, i.e. obtain oxygen doping nitrogen carbide-Doré metal photocatalysis composite；
A kind of application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst:
Taking 30 milligrams of oxygen doping nitrogen carbide-Doré metal photocatalysis composites and joining 40 milliliters of concentration is 6 millis
In the p-Nitrobromobenzene solution of grams per liter, ultrasonic disperse obtains suspension after 3 hours, adds 30 milligrams of ammonium formates of sacrifice agent and 30
After milligram ammonium oxalate, then in suspension, it is passed through nitrogen deoxygenation and as protection gas, puts into (the band of irradiation under simulated solar irradiation
Have the 300W xenon lamp more than 420 nm filter, Beijing Bo Feilai Science and Technology Ltd.), take a sample at regular intervals, survey
Trying this material photo-reduction performance to p-Nitrobromobenzene, after 2.5 hours, the conversion ratio of p-Nitrobromobenzene is about 80%, such as Fig. 4 institute
Show.
The foregoing is only the preferable case study on implementation of the present invention, all impartial changes done according to scope of the present invention patent
With modification, the covering scope of the present invention all should be belonged to.
Claims (10)
1. the preparation method of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, it is characterised in that described preparation method bag
Include following steps:
(1) nitrogen carbide is prepared；
(2) oxygen doping nitrogen carbide is prepared；
(3) oxygen doping nitrogen carbide-noble metal composite-material is prepared.
The preparation method of oxygen doping nitrogen carbide-noble metal composite photo-catalyst the most according to claim 1, its feature exists
In, described preparation method particularly as follows:
(1), after being calcined by carbon nitrogen source, nitrogen carbide, the suspension of preparation nitrogen carbide are obtained；
(2) suspension of nitrogen carbide step (1) prepared mixes with hydrogen peroxide, after hydro-thermal reaction, cools down, separates, washs,
It is dried, obtains oxygen doping nitrogen carbide, prepare the suspension of oxygen doping nitrogen carbide；
(3) suspension of the oxygen doping nitrogen carbide obtained is mixed with precious metal salt solution, stir 5-50 hour, then photo-reduction
Noble metal, centrifugation, washed product, i.e. obtain oxygen doping nitrogen carbide-noble metal photocatalysis composite.
The preparation method of oxygen doping nitrogen carbide-noble metal composite photo-catalyst the most according to claim 1 and 2, its feature
Being, carbon nitrogen source described in step (1) is selected from tripolycyanamide, cyanamid dimerization or carbamide one or more；Described calcining is concrete
For: calcine 48 hours at 450 650 DEG C.
4. according to the preparation method of the oxygen doping nitrogen carbide-noble metal composite photo-catalyst described in Claims 2 or 3, its feature
It is, after step (1) obtains nitrogen carbide, produces and grind, obtain powder, then be placed in ultrasonic disperse in alcoholic solvent, obtain nitrogen carbide
Suspension；Described alcoholic solvent is selected from methanol, ethanol, normal propyl alcohol, isopropanol, butanol, ethylene glycol, 1,2-propylene glycol, 1,3-the third two
One or more in alcohol or glycerol；The concentration of the suspension of described nitrogen carbide is 0.1 3mg/mL.
5. according to the preparation method of the oxygen doping nitrogen carbide-noble metal composite photo-catalyst described in Claims 2 or 3, its feature
Being, in step (2), the suspension of nitrogen carbide and the volume ratio of hydrogen peroxide are 0.1 3:1；The mass concentration of hydrogen peroxide is 10-
30%；Described hydrothermal reaction condition is: hydro-thermal reaction 3 15 hours at 100 180 DEG C.
6. according to the preparation method of the oxygen doping nitrogen carbide-noble metal composite photo-catalyst described in claim 2 or 5, its feature
Being, in step (2), the concentration of the suspension of gained oxygen doping nitrogen carbide is 0.1 10mg/mL.
7. according to the preparation method of the oxygen doping nitrogen carbide-noble metal composite photo-catalyst described in any one of claim 2-6, its
It is characterised by, one or more in gold chloride, sodium chloraurate, silver nitrate, silver acetate of slaine described in step (3),
Wherein in oxygen doping nitrogen carbide suspension, the quality of oxygen doping nitrogen carbide is 1 with the noble metal component ratio in precious metal salt solution:
0.0001–0.2。
8. according to the preparation method of the oxygen doping nitrogen carbide-noble metal composite photo-catalyst described in any one of claim 2-7, its
Being characterised by, photo-reduction noble metal described in step (3) is particularly as follows: by mixed liquor irradiation 35 hours, Qi Zhongzi under uviol lamp
The power of outer lamp is more than or equal to 50W.
9. oxygen doping nitrogen carbide-noble metal composite photo-catalyst, it is characterised in that use any one of claim 1-8 institute
The method stated prepares.
10. the application of oxygen doping nitrogen carbide-noble metal composite photo-catalyst, it is characterised in that to nitroaromatic
Photo catalytic reduction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142616A (en) * | 2017-04-19 | 2017-09-08 | 江苏大学 | A kind of preparation method of the nanofiber packaging material of degradable residues of pesticides |
| CN108355702A (en) * | 2018-03-23 | 2018-08-03 | 辽宁大学 | A kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst and its preparation method and application |
| CN108355698A (en) * | 2018-02-13 | 2018-08-03 | 西安理工大学 | A kind of preparation method of O doped graphites phase carbon nitride nanometer sheet powder |
| CN108404993A (en) * | 2018-03-15 | 2018-08-17 | 湖南大学 | A method of handling nitryl aromatic hydrocarbons using the carbonitride load type nano gold catalyst of poly-dopamine reduction |
| CN108658067A (en) * | 2018-06-20 | 2018-10-16 | 河北大学 | A kind of nitrogen co-doped carbon material of phosphorus and preparation method thereof and purposes |
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| CN111036275A (en) * | 2020-01-07 | 2020-04-21 | 南开大学 | Preparation and application method of oxygen-doped graphite-phase nitrogen carbide photolysis water-hydrogen production catalyst |
| CN112354555A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院地球环境研究所 | Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof |
| CN112705235A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Carbon-coated nickel carbide nano composite material and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011099A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical mesoporous carbon nitride material and preparation method thereof |
| CN103418415A (en) * | 2013-08-22 | 2013-12-04 | 南昌航空大学 | Method for using ultrasonic mixing to prepare Ag-g-C3N4/TiO2 photocatalyst |
| CN103623855A (en) * | 2013-11-12 | 2014-03-12 | 江苏大学 | Method for preparing carbon nitride/silver nano composite material by reduction with chemical reducer |
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN105642329A (en) * | 2016-01-01 | 2016-06-08 | 三峡大学 | Loaded graphite phase carbonized nitrogen composite material as well as preparation method and application thereof |
-
2016
- 2016-07-28 CN CN201610605543.5A patent/CN106238085A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011099A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical mesoporous carbon nitride material and preparation method thereof |
| CN103418415A (en) * | 2013-08-22 | 2013-12-04 | 南昌航空大学 | Method for using ultrasonic mixing to prepare Ag-g-C3N4/TiO2 photocatalyst |
| CN103623855A (en) * | 2013-11-12 | 2014-03-12 | 江苏大学 | Method for preparing carbon nitride/silver nano composite material by reduction with chemical reducer |
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN105642329A (en) * | 2016-01-01 | 2016-06-08 | 三峡大学 | Loaded graphite phase carbonized nitrogen composite material as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| YONGSHENG FU ET AL: "Ag/g-C3N4 catalyst with superior catalytic performance for the degradation of dyes: a borohydride-generated superoxide radical approach", 《NANOSCALE》 * |
| 张金水等: "石墨相氮化碳的化学合成及应用", 《物理化学学报》 * |
| 王俊虎: "石墨相氮化碳的制备、改性及其光催化性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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| CN112705235A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Carbon-coated nickel carbide nano composite material and preparation method and application thereof |
| CN112705235B (en) * | 2019-10-24 | 2023-08-08 | 中国石油化工股份有限公司 | Carbon-coated nickel carbide nanocomposite and preparation method and application thereof |
| CN111036275A (en) * | 2020-01-07 | 2020-04-21 | 南开大学 | Preparation and application method of oxygen-doped graphite-phase nitrogen carbide photolysis water-hydrogen production catalyst |
| CN111036275B (en) * | 2020-01-07 | 2022-08-05 | 南开大学 | Preparation and application method of oxygen-doped graphite-phase nitrogen carbide photolysis water-hydrogen production catalyst |
| CN112354555A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院地球环境研究所 | Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof |
| CN112354555B (en) * | 2020-11-09 | 2022-03-11 | 中国科学院地球环境研究所 | Metal monatomic supported carbon-nitrogen polymer catalyst and preparation method thereof |
| CN113578381A (en) * | 2021-07-22 | 2021-11-02 | 江苏科技大学 | Oxygen-doped nitrogenated carbohydrate gel, preparation method thereof and application of oxygen-doped nitrogenated carbohydrate gel in degrading formaldehyde |
| CN113578381B (en) * | 2021-07-22 | 2024-02-27 | 江苏科技大学 | Oxygen-doped carbon nitride hydrogel, preparation method thereof and application of oxygen-doped carbon nitride hydrogel in formaldehyde degradation |
| CN115282983A (en) * | 2022-07-14 | 2022-11-04 | 金陵科技学院 | Indium zinc sulfide supported noble metal photocatalyst and preparation method and application thereof |
| CN115282983B (en) * | 2022-07-14 | 2023-08-22 | 金陵科技学院 | Photocatalyst of indium zinc sulfide loaded with noble metal, preparation method and application thereof |
| CN115518666A (en) * | 2022-09-20 | 2022-12-27 | 江苏大学 | Preparation method and application of ammonium formate modified coral-shaped wide-spectral-response carbon-nitrogen polymer photocatalyst |
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