CN109012728A - Catalytic oxidation-reduction synthesis peroxidating catalyst for hydrogen and preparation method thereof under visible light - Google Patents
Catalytic oxidation-reduction synthesis peroxidating catalyst for hydrogen and preparation method thereof under visible light Download PDFInfo
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- CN109012728A CN109012728A CN201810907853.1A CN201810907853A CN109012728A CN 109012728 A CN109012728 A CN 109012728A CN 201810907853 A CN201810907853 A CN 201810907853A CN 109012728 A CN109012728 A CN 109012728A
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- potassium
- catalyst
- carbon nitride
- hydrogen
- visible light
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 230000033116 oxidation-reduction process Effects 0.000 title claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical group [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- -1 phosphoric acid hydrogen Chemical class 0.000 claims description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims 2
- 238000002242 deionisation method Methods 0.000 claims 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 235000007715 potassium iodide Nutrition 0.000 claims 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 1
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 1
- 235000011151 potassium sulphates Nutrition 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 40
- 239000012071 phase Substances 0.000 abstract description 14
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 150000007974 melamines Chemical class 0.000 abstract 1
- 150000003672 ureas Chemical class 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910010298 TiOSO4 Inorganic materials 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalyst technical field, catalytic oxidation-reduction synthesis peroxidating catalyst for hydrogen and preparation method thereof under specially a kind of visible light.Catalyst of the present invention is the graphite phase carbon nitride catalyst of a kind of phosphorus, potassium doping, and graphite phase carbon nitride material source is introduced in situ in urea thermal polymerization, is doped in the skeleton structure of graphite phase carbon nitride in urea thermal polymerization, phosphorus, potassium element.The present invention, to the facilitation of graphite phase carbon nitride, realizes that catalytic oxidation-reduction synthesizes hydrogen peroxide in visible light, room temperature, normal pressure liquid-phase system using doping component.The graphite phase carbon nitride catalyst of the co-modified urea thermal polymerization preparation of phosphorus, potassium shows higher catalytic activity in photocatalytic-oxidation reduction synthesis hydroperoxidation under visible light compared with the graphite phase carbon nitride catalyst of the co-modified melamine thermal polymerization preparation of existing phosphorus, potassium.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to for catalytic oxidation-reduction synthesis in liquid-phase system under visible light
Catalyst of hydrogen peroxide and preparation method thereof.
Background technique
Hydrogen peroxide (H2O2) as a kind of environmental-friendly oxidant, it is widely used in medical treatment, wastewater treatment, papermaking, spinning
It knits, the industries such as electronics industry.There is traditional " anthraquinone autooxidation method " production hydrogen peroxide energy consumption height, byproduct of reaction to pollute ring
The disadvantages of border, high production cost (Angew. Chem. Int. Ed., 2006,45,6962; ChemSusChem,2016,
9,3374).With this multi-step, high consumption production process compared with, using one-step method by hydrogen (H2) oxygen (O2) directly synthesize
H2O2Have many advantages, such as that technical process is simple, environmental-friendly, raw material economics.Existing research shows that palladium (Pd) base catalyst has very
Good hydrogen-oxygen directly synthesizes H2O2Performance (Science, 2009,323,1037;Science, 2016,351,965).So
And hydrogen-oxygen directly synthesizes H2O2Technique there are potential risk of explosion.Therefore, new type of safe, environmental-friendly H are developed2O2It closes
There is important practical significance at route.
The method of photoactivation converts light energy into hydrogen peroxide, has both been able to achieve to stablize this renewable energy of luminous energy and store up
Hiding, and luminous energy can directly be changed to the chemicals for switching to high added value.In recent years, pass through the photo catalytic reduction molecule in liquid-phase system
The research of oxygen synthesis hydrogen peroxide at home and abroad has been reported that.Semiconductor oxide zinc (ZnO), titanium dioxide (TiO2) photocatalysis material
Material can catalyze and synthesize the H of millimolar concentration grade under ultraviolet light2O2(Environ. Sci. Technol., 1988,22,
798;Environ. Sci. Technol., 1994,28,776).Work as TiO2Load gold, silver (such as Au/TiO2、AuAg/
TiO2) after, ultraviolet catalytic activity can be obviously improved (J. Am. Chem. Soc., 2010,132,7850; ACS
Catal., 2012,2,599).However, main group of sunlight becomes visible light (nm of λ > 420), design synthesis is visible
The lower catalysis material with high activity of light irradiation is the important channel for improving phototransformation efficiency.Under simulated visible light irradiation,
Nanogold particle is carried on BiVO4Or the TiO of carbonate modification2Surface is with higher to catalyze and synthesize H2O2Activity (ACS
Catal., 2016, 6, 4976;Angew. Chem.Int. Ed., 2016,55,12773).
Graphite phase carbon nitride material is a kind of nonmetallic organic polymer catalysis material, mainly by C abundant in the earth's crust,
N, H element is constituted, and (Angew. can be synthesized by way of thermal polymerization with the cheap raw material such as melamine, cyanamide, urea
Chem. Int. Ed., 2012,51,68).Carbon nitride material is widely used for Photocatalyzed Hydrogen Production, hydrogen reduction, You Jihe
At the research of, organic matter degradation etc., show higher photocatalytic activity and stability (Adv. Mater., 2015,
27, 2150;ACS Catal., 2012,2,1596).Hirai etc. is using melamine as carbon nitride precursor, to carbonitride
The nonmetallic ingredients such as middle introducing pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride are modified, and obtained carbon nitride material has
Higher photocatalytic-oxidation reduction synthesis it is hydrogen peroxide activated (J. Am. Chem. Soc., 2016,138,10019;ACS
Catal., 2016,6,7021).Choi etc. passes through thermal polymerization after mixing with dipotassium hydrogen phosphate using melamine as presoma
Mode made from KDP-CN-7.5 catalyst under visible light after catalytic oxidation-reduction 12h, the concentration of hydrogen peroxide can achieve 3
mmol L–1(ACS Catal., 2017,7,2886).
Photocatalytic-oxidation reduction synthesis hydrogen peroxide method has compared with the direct process for catalytic synthesis of hydrogen-oxygen without explosion wind
The remarkable advantages such as danger, normal temperature and pressure operation.The low concentration hydrogen peroxide of catalytic oxidation-reduction synthesis can be applied directly under visible light
In fields such as medical sterilization, sewage treatments, it can be achieved that the distributed green production in situ of hydrogen peroxide and green application, effectively subtract
Lack its security risk during transportation.
Summary of the invention
It is an object of the invention to propose a kind of to can be used under visible light urging in liquid-phase system with good catalytic
Change the catalyst of hydrogen reduction synthesis hydrogen peroxide, and proposes the preparation method of the catalyst.
The catalyst provided by the invention that can be used for photocatalytic-oxidation reduction synthesis hydrogen peroxide in liquid-phase system is a kind of non-
The graphite phase carbon nitride catalyst that noble metal catalyst --- phosphorus, potassium adulterate；By the carbon of rich content, nitrogen, phosphorus, potassium, oxygen in the earth's crust
Element composition, wherein graphite phase carbon nitride material source draws in urea thermal polymerization, phosphorus, potassium element in urea thermal polymerization in situ
Into being doped in the skeleton structure of graphite phase carbon nitride.
The preparation method of the catalyst of oxygen reduction synthesis hydrogen peroxide is catalyzed under above-mentioned visible light proposed by the present invention, specifically
Step are as follows:
(1) urea and sylvite or phosphate are weighed, is ground in aluminium oxide mortar uniform；
(2) it is put into the alumina crucible with cover of aluminium foil package；The crucible for filling precursor mixture is placed in Muffle furnace, is risen
Temperature is to 400 ~ 650 DEG C, and preferably 450 ~ 550 DEG C, heating rate is 1 ~ 15 DEG C per minute, and preferably 2 ~ 10 DEG C per minute, still air
Middle holding 1 ~ 6 h, preferably 2 ~ 4 h, Temperature fall obtain faint yellow or yellow sample；
(3) then, gained bulk sample is placed in aluminium oxide mortar, grinding uniformly, makes it at powdered；It disperses powder in
In deionized water, the usage ratio of sample and water is 0.8-1.2g:1 L, preferably 1 g:1 L, the ultrasound removing 1 under ultrasonic wave
~3h；
(4) it finally, sample is washed with deionized for several times, and is filtered by vacuum with 0.45 μm of filter membrane, the 55-65 in vacuum drying oven
10-15h is dried at DEG C, dry 12h at preferably 60 DEG C obtains the graphite phase carbon nitride catalyst of phosphorus, potassium doping.
In the present invention, the ratio of the urea and sylvite or phosphatic amount is with 10.0 g urea for 1 unit, then right
The sylvite answered or phosphatic amount are 1 ~ 15 mmol, preferably 5 ~ 10 mmol.
In the present invention, the sylvite is selected from potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, potassium bromide, potassium iodide, sulphur
Sour potassium, potassium acetate, Potassium Hydrogen Phthalate, potassium oxalate.
In the present invention, the phosphate is selected from potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, disodium hydrogen phosphate, phosphoric acid
Dihydro lithium, ammonium dihydrogen phosphate.
The catalytic performance of catalyst provided by the invention can be evaluated with the following method:
100mg catalyst is weighed in the mixed solution that 90mL deionized water and 10mL ethyl alcohol form, ultrasonic disperse 2 minutes.It will
The above suspension containing catalyst sample is transferred to 300 mL, in the photo catalysis reactor with quartzy top cover.It is anti-in photocatalysis
Before should carrying out, first it is continually fed into oxygen into suspension 20 minutes, so that the oxygen in liquid phase is reached saturation, then open xenon lamp
Light source is about 300mWcm by ending the intensity of incident light of color filter (λ >=420nm)–2.Solution temperature passes through cooling cycle
Water installations control keeps oxygen to be continually fed into during 25 DEG C, evaluating catalyst.Product hydrogen peroxide is dense in reaction solution
Degree is according to Beer-Lambert law, with TiOSO4/H2SO4After reagent complexing, pass through light splitting using ultraviolet-uisible spectrophotometer
Photometry measurement.
Compared with prior art, the beneficial effects are mainly reflected as follows following three aspects:
(1) hydrogen peroxide preparation method proposed by the present invention has environment friend compared with " anthraquinone ", hydrogen-oxygen direct synthesis technique
The remarkable advantages such as good, not easy to explode, normal temperature and pressure operation.The low concentration hydrogen peroxide synthesized simultaneously by the technique can be answered directly
For fields such as medical sterilization, sewage treatments, realizes the distributed green production in situ and green application of hydrogen peroxide, reduce fortune
Defeated security risk；
(2) graphite phase carbon nitride material proposed by the present invention be non-precious metal catalyst, prepared by urea thermal polymerization, raw material at
This is low, and the elements such as phosphorus, potassium of doping rich content in the earth's crust, from a wealth of sources, catalyst is low in cost；
(3) reaction proposed by the present invention carries out under room temperature, normal pressure, visible light, is conducive to the utilization efficiency for improving sunlight.It urges
Agent reaction system is the heterogeneous liquid-phase catalysis system of ethyl alcohol, deionized water composition, and catalyst realizes recycling in which can be convenient
It utilizes, reaction stability is good.
Detailed description of the invention
Fig. 1 is the TEM electromicroscopic photograph of catalyst of the present invention.
Fig. 2 is that the XRD of catalyst of the present invention is composed.
Fig. 3 is the reaction result of different catalysts visible light catalytic hydrogen reduction hydroperoxidation active testing example.
Specific embodiment
The invention is further illustrated by the following examples, but not thereby limiting the invention.
Embodiment 1:
Weigh 10.0 g urea and 10 mmol dipotassium hydrogen phosphate (K2HPO4·3H2O), grind uniformly, make in aluminium oxide mortar
It is sufficiently mixed, and is transferred in 50mL alumina crucible.The crucible for filling presoma is placed in Muffle furnace, per minute with 3 DEG C
Rate be warming up to 450 DEG C, keep 2h in still air, Temperature fall obtains the graphite phase carbon nitride material of phosphorus, potassium doping,
Sample is faint yellow.It is scattered in it in deionized water, the use of sample and water in powdered the grinding of gained bulk sample
Amount ratio is 1 g:1 L, and 3.0 h are removed under ultrasound, is filtered by vacuum with 0.45 μm of filter membrane, is washed, taken out repeatedly with deionized water
Filter is for several times.It filters gained sample and dries 12h at 60 DEG C in vacuum drying oven to get CNKP-10 catalyst.The TEM of the catalyst
Electromicroscopic photograph is shown in Fig. 1, and the XRD spectrum of the catalyst is shown in Fig. 2.
Embodiment 2:
By the dipotassium hydrogen phosphate (K in embodiment 12HPO4·3H2O) it is changed to potassium phosphate (K3PO4), other preparation conditions are the same as real
Apply example 1.Gained catalyst is denoted as CNK3P-10.
Embodiment 3:
By the dipotassium hydrogen phosphate (K in embodiment 12HPO4·3H2O) it is changed to disodium hydrogen phosphate (Na2HPO4), other prepare item
Part is the same as embodiment 1.Gained catalyst is denoted as CNNaP-10.
Embodiment 4:
By the dipotassium hydrogen phosphate (K in embodiment 12HPO4·3H2O) it is changed to potassium acetate (CH3COOK), other preparation conditions are same
Embodiment 1.Gained catalyst is denoted as CNCK-10.
Embodiment 5:
By the dipotassium hydrogen phosphate (K in embodiment 12HPO4·3H2O it) is changed to potassium iodide (KI), the same embodiment of other preparation conditions
1.Gained catalyst is denoted as CNKI-10.
Comparative example 1:
Weigh 10.0 g urea ground in aluminium oxide mortar be uniformly put into aluminium foil package alumina crucible with cover in.It will contain
There is the crucible of presoma to be placed in Muffle furnace, is warming up to 450 DEG C with 3 DEG C of rates per minute, 2h is kept in still air, it is natural
Cooling obtains faint yellow sample.It is scattered in it in deionized water, sample in powdered the grinding of gained bulk sample sample
The usage ratio of product and water is 1 g:1 L, removes 3h under ultrasonic wave, is filtered by vacuum with 0.45 μm of filter membrane, anti-with deionized water
After backwashing is washed, is filtered for several times.It filters gained sample and dries 12h, the graphite-phase nitrogen not adulterated at 60 DEG C in vacuum drying oven
Change C catalyst, be named as GCN catalyst, the XRD spectrum of the catalyst is shown in Fig. 2.
Visible light catalytic hydrogen reduction hydroperoxidation active testing example 1:
It weighs 100mg CNKP-10 catalyst to be placed in the mixed solution of 90mL deionized water and 10mL ethyl alcohol, ultrasonic disperse 2 divides
Clock.The above suspension solution is transferred to 300 mL, in the photo catalysis reactor with quartzy top cover.It is carried out in light-catalyzed reaction
Before, suspension is first led into oxygen 20 minutes, is saturated the oxygen in liquid phase, and controls reactor temperature by cooling cycle water installations
Degree is 25 DEG C, then opens xenon source (Ceaulight, CEL-HXUV300), passes through cut-off color filter (λ >=420nm)
The intensity of incident light is about 300mWcm–2, and oxygen is kept to be continually fed into, flow is about 20mL/min.Product mistake in reaction solution
The concentration of hydrogen oxide is according to Beer-Lambert law, with TiOSO4/H2SO4After reagent complexing, UV, visible light spectrophotometric is used
(Shimadzu UV-1800) is counted to measure by spectrophotometry.Reaction result produces as shown in figure 3, after illumination reaction 10 hours
The concentration of object hydrogen peroxide reaches 5 mmol L–1, hence it is evident that be higher than document in using melamine as presoma, by with phosphoric acid hydrogen two
Hydrogen peroxide concentration (ACS of the KDP-CN-7.5 catalyst made from the mode of thermal polymerization in the longer reaction time after potassium mixing
Catal., 2017,7,2886).
Visible light catalytic hydrogen reduction synthesizes hydroperoxidation active testing example 2:
Using CNK3P-10 as catalyst, other conditions are with visible light catalytic hydrogen reduction hydroperoxidation active testing example 1, instead
Should result be shown in Fig. 3.
Visible light catalytic hydrogen reduction synthesizes hydroperoxidation active testing example 3:
Using CNNaP-10 as catalyst, other conditions are with visible light catalytic hydrogen reduction hydroperoxidation active testing example 1, instead
Should result be shown in Fig. 3.
Visible light catalytic hydrogen reduction synthesizes hydroperoxidation active testing example 4:
Using CNCK-10 as catalyst, other conditions are with visible light catalytic hydrogen reduction hydroperoxidation active testing example 1, instead
Should result be shown in Fig. 3.
Visible light catalytic hydrogen reduction synthesizes hydroperoxidation active testing example 5:
Using CNKI-10 as catalyst, other conditions are with visible light catalytic hydrogen reduction hydroperoxidation active testing example 1, instead
Should result be shown in Fig. 3.
Visible light catalytic hydrogen reduction synthesizes hydroperoxidation active testing comparative example 1:
Using GCN as catalyst, other conditions are the same as visible light catalytic hydrogen reduction hydroperoxidation active testing example 1, reaction knot
Fruit is shown in Fig. 3.
Claims (5)
1. catalytic oxidation-reduction synthesizes peroxidating catalyst for hydrogen under a kind of visible light, which is characterized in that be that a kind of phosphorus, potassium adulterate
Graphite phase carbon nitride catalyst is made of carbon, nitrogen, phosphorus, potassium, oxygen element；Wherein, graphite phase carbon nitride material source is in urea warm
Polymerization, phosphorus, potassium element are introduced in situ in urea thermal polymerization, are doped in the skeleton structure of graphite phase carbon nitride.
2. the preparation method of catalytic oxidation-reduction synthesis peroxidating catalyst for hydrogen under a kind of visible light as described in claim 1,
It is characterized in that, specific steps are as follows:
(1) urea and sylvite or phosphate are weighed, is ground in mortar uniform；
(2) it is put into the alumina crucible with cover of aluminium foil package；The crucible for filling precursor mixture is placed in Muffle furnace, is risen
For temperature to 400 ~ 650 DEG C, heating rate is 1 ~ 15 DEG C per minute, 1 ~ 6 h is kept in still air, Temperature fall obtains faint yellow
Or yellow sample；
(3) then, gained bulk sample is placed in mortar, grinding uniformly, makes it at powdered；Deionization is dispersed by powder
In water, the usage ratio of sample and water is (0.8-1.2): 1 g/L, 1 ~ 3h of ultrasound removing under ultrasonic wave；
(4) it finally, sample is washed with deionized for several times, and is filtered by vacuum with 0.45 μm of filter membrane, the 55-65 in vacuum drying oven
Dry 10-15h at DEG C, obtains the graphite phase carbon nitride catalyst of phosphorus, potassium doping.
3. preparation method according to claim 2, which is characterized in that the urea and sylvite or phosphatic amount
Than with 10.0 g urea for 1 unit, corresponding sylvite or phosphatic amount are 1 ~ 15 mmol.
4. preparation method according to claim 2, which is characterized in that the sylvite is selected from potassium dihydrogen phosphate, phosphoric acid hydrogen
Dipotassium, potassium phosphate, potassium bromide, potassium iodide, potassium sulfate, potassium acetate, Potassium Hydrogen Phthalate, potassium oxalate.
5. preparation method according to claim 2, which is characterized in that the phosphate is selected from potassium dihydrogen phosphate, phosphoric acid
Hydrogen dipotassium, potassium phosphate, disodium hydrogen phosphate, lithium dihydrogen phosphate, ammonium dihydrogen phosphate.
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