CN111185244A - Organic-inorganic composite nano photocatalyst and preparation method thereof - Google Patents
Organic-inorganic composite nano photocatalyst and preparation method thereof Download PDFInfo
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- CN111185244A CN111185244A CN202010032888.2A CN202010032888A CN111185244A CN 111185244 A CN111185244 A CN 111185244A CN 202010032888 A CN202010032888 A CN 202010032888A CN 111185244 A CN111185244 A CN 111185244A
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- metal phthalocyanine
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- inorganic composite
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 69
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- -1 nitro-substituted phthalonitrile Chemical class 0.000 claims abstract description 22
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 13
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 3
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical group [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940079721 copper chloride Drugs 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 32
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011206 ternary composite Substances 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 229910052725 zinc Inorganic materials 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- WBLCQMXLGKWTAV-UHFFFAOYSA-N 4-(3,4-dicyanophenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C#N)C(C#N)=C1 WBLCQMXLGKWTAV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
-
- 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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an organic-inorganic composite nano photocatalyst, which comprises the steps of taking nitro-substituted phthalonitrile and p-hydroxybenzoic acid as raw materials, preparing 4-carboxyl phenoxy-substituted metal phthalocyanine through two-step reaction, and compounding the metal phthalocyanine, graphene oxide and molybdenum disulfide to obtain a metal phthalocyanine, graphene and molybdenum disulfide ternary composite photocatalyst; the invention can effectively improve the solubility of the metal phthalocyanine by introducing the p-carboxyl phenoxy group on the branched chain of the metal phthalocyanine so as to improve the dispersing ability of the metal phthalocyanine as a photocatalyst in a reaction system, and forms the organic-inorganic composite nano photocatalyst by compounding the metal phthalocyanine with the graphene and the molybdenum disulfide, and the three components have synergistic effect, thereby not only improving the light absorption ability and widening the light absorption range, but also being beneficial to increasing the active sites of the catalyst and improving the catalytic activity.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to an organic-inorganic composite nano photocatalyst and a preparation method thereof.
Background
The phthalocyanine is a plane large ring conjugated system composed of four isoindole units, the phthalocyanine molecule is a sixteen-membered ring composed of eight carbon atoms and eight nitrogen atoms alternately, and is a plane large pi-bond conjugated aromatic system with 18 pi electrons, the structure is very stable, and the lengths of all C-H bonds are almost equal. Meanwhile, the phthalocyanine ring is internally provided with 1 cavity which can contain a plurality of transition metal atoms such as cobalt, copper, iron, nickel, zinc and the like, the bonding force of the metal ions and the phthalocyanine is strong, the chemical property is stable, the metal phthalocyanine compound has strong transition in a visible light area and is easy to generate an excited state, and the metal phthalocyanine compound is a visible light catalyst which is energy-saving, green and has a very good application prospect.
In a photocatalytic system, a promoter plays an extremely important role in reducing the activation energy or overpotential of a semiconductor surface reaction, promoting the separation of photogenerated carriers at a promoter/semiconductor interface, and inhibiting the photo-corrosion of a semiconductor to enhance the photostability of the semiconductor. The graphene being a C atom sp2The 2D carbon network with the hybrid hexagonal structure is similar to a conjugated structure formed by connecting an infinite number of benzene rings, the unique structure of graphene determines that the graphene has a plurality of excellent performances in the aspects of electricity, heat, mechanics, optics and the like, perfect defect-free single-layer graphene is almost completely transparent, but can absorb 2.3% of visible light, and the transmittance is 97.7%. The 2D characteristic of the ultrathin single-layer graphene also has a huge specific surface area, and the theoretical calculation value is 2630m2g-1The photocatalyst has great advantages and wide application in the aspect of loading of the catalyst, the forbidden band width and the photoresponse range of the molybdenum disulfide can be effectively adjusted, the absorption utilization rate of sunlight is improved, stronger light stability is achieved, and the molybdenum disulfide can effectively improve the catalytic efficiency of the photocatalyst.
However, the existing metal phthalocyanine has poor solubility due to a macromolecular conjugated system, so that the metal phthalocyanine is difficult to uniformly disperse in a catalytic system, and the catalytic performance of single molybdenum disulfide as a photocatalyst is not ideal, and a molybdenum disulfide material needs to be modified to improve the catalytic efficiency.
Disclosure of Invention
The invention aims to provide an organic-inorganic composite nano photocatalyst and a preparation method thereof, wherein the solubility of metal phthalocyanine can be effectively improved by introducing carboxyl phenoxy on a branched chain of the metal phthalocyanine, so that the dispersing capacity of the metal phthalocyanine as the photocatalyst in a reaction system is improved, the organic-inorganic composite nano photocatalyst is formed by compounding the metal phthalocyanine with graphene and molybdenum disulfide, and the three components have synergistic effect, so that the light absorption capacity is improved, the light absorption range is widened, the active sites of the catalyst are increased, and the catalytic activity is improved.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an organic-inorganic composite nano photocatalyst specifically comprises the following steps:
(1) under the protection of nitrogen, adding dimethyl sulfoxide into a reaction bottle, adding nitro-substituted phthalonitrile and p-hydroxybenzoic acid under stirring, adding potassium carbonate, stirring and reacting for 20-30h at 25-35 ℃, then dropwise adding the reaction liquid into deionized water, adjusting the pH value to 1 by using concentrated hydrochloric acid, separating out flocculent precipitate, filtering and separating the precipitate, washing by using deionized water, recrystallizing by using methanol, and then placing in a vacuum drying oven for drying to obtain a phthalonitrile intermediate, wherein cyano is an electron-withdrawing group, so that the nitro in the ortho-para position of the cyano is active and easy to be substituted, in dimethyl sulfoxide, p-hydroxybenzoic acid reacts with potassium carbonate to generate a potassium salt compound, potassium phenolate easily reacts with the nitro in the ortho-para position of the cyano, the nitro falls off and generates ether bonds, and the reaction equation is as follows:
(2) under the protection of nitrogen, the phthalonitrile intermediate obtained in the step (1) and MXnDissolving in n-amyl alcohol, heating to 40-50 deg.C, adding 1, 8-diazabicycloundec-7-ene (DBU), heating to 100 deg.C and 130 deg.C, reacting for 4-6 hr, cooling to room temperature, adding hydrochloric acid into the reaction liquor to regulate pH value to 1-3, producing lots of flocculent precipitate in the reaction liquor, adding n-amyl alcohol, stirring, drying, and making it obtainFiltering the reaction solution, washing the filter cake to be neutral by using deionized water, drying in vacuum and grinding to obtain metal phthalocyanine powder, wherein the reaction equation is as follows:
in the synthesis process, the phthalonitrile intermediate undergoes electronic rearrangement at high temperature to generate an imine intermediate (a), the imine intermediate is complexed with metal ions to generate a coordination intermediate (b) in the presence of a catalyst DBU, one nitrogen atom of the imine intermediate (a) is negatively charged, one carbon atom of the imine intermediate (a) is positively charged and is in an amphoteric dipole state, and the two nitrogen atoms can react with each other to form a covalent bond between the carbon atom and the nitrogen atom, when MX is usednIn the case of transition metal salts, the coordination ability of metal ions is strong, so that phthalocyanine compounds are generated, and the reaction mechanism is as follows:
the p-carboxyl phenoxy is introduced into phthalonitrile molecules, and then the p-carboxyl phenoxy is substituted for phthalonitrile to synthesize the metal phthalocyanine compound, so that carboxyl and ether bonds are smoothly introduced into the metal phthalocyanine molecules, the solubility of the metal phthalocyanine is greatly improved, the solubility of the metal phthalocyanine in a water phase and an organic phase is obviously improved, the dispersibility of the metal phthalocyanine serving as a photocatalyst in a reaction system is improved, and the catalytic activity is favorably improved.
(3) Respectively dissolving the metal phthalocyanine powder and graphene oxide obtained in the step (2) in chloroform to obtain a metal phthalocyanine solution and a graphene oxide solution, and then mixing the metal phthalocyanine solution and the graphene oxide solution according to a volume ratio of 1: 0.5-1, ultrasonic dispersing for 0.5-2h, filtering, vacuum concentrating the filtrate, and drying to obtain graphene oxide-metal phthalocyanine compound, wherein the graphene is carbon atom sp2The 2D carbon network with a hybrid hexagonal structure has high specific surface area and excellent conductivity, and the graphene is used as a composite material, so that agglomeration can be prevented, and the electron transfer capacity of the catalyst can be improved, and the metal phthalocyanine and the graphene have the function ofHas pi-pi acting force, so that the product can be well dispersed in the solvent. Meanwhile, carboxyl in the metal phthalocyanine can form hydrogen bonds with hydroxyl groups in the graphene, and GO is modified through non-covalent bonds, namely the conjugated structure of GO is not damaged, and meanwhile, the performance is preserved;
(4) dissolving sodium dodecyl benzene sulfonate in deionized water, adding sodium molybdate, thiourea and the graphene oxide-metal phthalocyanine compound obtained in the step (3), ultrasonically dispersing and stirring for 0.5-1h, transferring the dispersion liquid into a high-pressure reaction kettle, reacting at 180 ℃ for 20-30h, naturally cooling to room temperature, sucking out supernatant in the reaction liquid to obtain bottom fixed powder, washing with the deionized water for 3 times, drying in an oven at 80-90 ℃ for 10-16h, grinding to obtain the organic-inorganic composite nano photocatalyst, wherein molybdenum disulfide is a typical layered metal sulfide, the molybdenum disulfide prepared by the conventional method is in a multilayer stacked state, the exposure of active sites of molybdenum disulfide catalysis is prevented, the photocatalytic efficiency of the molybdenum disulfide is severely limited, the compound of metal phthalocyanine and graphene is added in the process of preparing the molybdenum disulfide, the composite of the metal phthalocyanine and the graphene is used as a substrate for nucleation and growth of the molybdenum disulfide nanosheets, the precursor of the molybdenum disulfide can interact with oxygen-containing functional groups on the graphene, so that the size of the molybdenum disulfide nanosheets is effectively controlled by a constraint effect in the 2D graphene layer, and the active sites of the molybdenum disulfide are exposed due to the large porosity and the large specific surface area of the graphene, so that the photocatalytic activity of the molybdenum disulfide can be effectively improved, and meanwhile, the excellent light absorption performance of the metal phthalocyanine can enable the three to play a synergistic effect, so that the photocatalytic performance is improved.
Preferably, the molar ratio of 4-nitrophthalonitrile, p-hydroxybenzoic acid and potassium carbonate in step (1) is 1: 2-3:2-4, adding 10-20mL of dimethyl sulfoxide into each gram of 4-nitrophthalonitrile.
Preferably, MX is as described in step (1)nIs selected from one of ferrous chloride, cobalt chloride, copper chloride, cuprous chloride, zinc chloride, nickel acetate and cobalt acetate, and the nitro-substituted phthalonitrile is 3-nitrophthalonitrile or 4-nitrophthalonitrile.
Preferably, the molar ratio of the phthalonitrile intermediate to the metal chloride in step (2) is 1: 2-4, 10-20mL of n-pentanol and 1-2mL of 1, 8-diazabicycloundecen-7-ene are added per gram of phthalonitrile intermediate.
Preferably, the concentration of the metal phthalocyanine solution in the step (3) is 8-10mg/mL, and the concentration of the graphene oxide solution is 2-4 mg/mL.
Preferably, the preparation method of the graphene oxide in the step (3) comprises the following steps:
s1, adding concentrated sulfuric acid into a reaction bottle, cooling to 0-5 ℃, adding graphite and sodium nitrate, stirring for 20-40min, adding potassium permanganate at 10-20 ℃, and stirring to react for 1-2h after the addition is finished to obtain a first solution;
s2, heating the first solution to 30-40 ℃, stirring and reacting for 0.5-1h, then adding deionized water into the solution, heating to 90-100 ℃, continuing to react for 20-40min, then adding a hydrogen peroxide solution with the mass fraction of 5% into the solution, stirring uniformly, filtering, washing a filter cake with deionized water until the filter cake does not contain sulfate ions, and placing the filter cake in a vacuum drying oven for drying for 20-40h to obtain graphite oxide;
s3, crushing and grinding the graphite oxide obtained in the step S2, dissolving the graphite oxide in water, performing ultrasonic treatment for 10-20min, centrifuging for 10-20min at 6000-7000r/min, taking supernatant, heating to remove excessive moisture, and drying at 60 ℃ for 20-40h to obtain the graphene oxide.
Preferably, in S1, the mass ratio of graphite to sodium nitrate to potassium permanganate is 1: 0.4-0.6: 2-4, 20-30mL of concentrated sulfuric acid is used per gram of graphite, 20-30mL of deionized water and 2-3mL of hydrogen peroxide solution are added per gram of graphite in S2, and 80-150mL of deionized water is used per gram of graphite oxide in S3.
Preferably, the mass ratio of the sodium molybdate, the thiourea, the sodium dodecyl benzene sulfonate and the graphene oxide-metal phthalocyanine compound in the step (4) is 1: 0.8-1.2: 0.1-0.3: 2-5.
The invention has the beneficial effects that:
the p-carboxyl phenoxy is introduced into phthalonitrile molecules, and then the p-carboxyl phenoxy is substituted for phthalonitrile to synthesize a metal phthalocyanine compound, so that carboxyl and ether bonds are smoothly introduced into the metal phthalocyanine molecules, the solubility of the metal phthalocyanine is greatly improved, the solubility of the metal phthalocyanine in a water phase and an organic phase is obviously improved, the dispersibility of the metal phthalocyanine serving as a photocatalyst in a reaction system is improved, and the catalytic activity is favorably improved;
the graphene being a carbon atom sp2The 2D carbon network with the hybrid hexagonal structure has high specific surface area and excellent conductivity, the graphene is used as a composite material, agglomeration can be prevented, the electron transfer capacity of the catalyst can be improved, and the product can be well dispersed in a solvent due to pi-pi acting force between the metal phthalocyanine and the graphene. Meanwhile, carboxyl in the metal phthalocyanine can form hydrogen bonds with hydroxyl groups in graphene, GO is modified through non-covalent bonds, namely the conjugated structure of GO is not damaged, and the performance is preserved, molybdenum disulfide is a typical layered metal sulfide, molybdenum disulfide prepared through a conventional method is in a multilayer stacking state, the exposure of an active site catalyzed by molybdenum disulfide is hindered, the photocatalytic efficiency of molybdenum disulfide is severely limited, a compound of the metal phthalocyanine and the graphene is added in the preparation process of the molybdenum disulfide, the compound of the metal phthalocyanine and the graphene is used as a substrate for nucleation and growth of molybdenum disulfide nanosheets, a precursor of the molybdenum disulfide can interact with an oxygen-containing functional group on the graphene, the size of the molybdenum disulfide nanosheets is effectively controlled by a constraint effect in a 2D graphene layer, and the porosity of the graphene is high, the specific surface area is large, so that the active sites of the molybdenum disulfide are exposed, the photocatalytic activity of the molybdenum disulfide can be effectively improved, and meanwhile, the excellent light absorption performance of the metal phthalocyanine can enable the molybdenum disulfide, the molybdenum disulfide and the metal phthalocyanine to play a synergistic effect, so that the photocatalytic performance is improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of zinc phthalocyanine
Under the protection of nitrogen, adding 50mL of dimethyl sulfoxide into a reaction bottle, adding 4g of 4-nitrophthalonitrile and 7g of p-hydroxybenzoic acid under stirring, adding 15g of potassium carbonate, reacting for 24 hours under stirring at 30 ℃, then dropwise adding the reaction liquid into 150mL of deionized water, adjusting the pH value to 1 by using concentrated hydrochloric acid, separating out flocculent precipitate, carrying out suction filtration and separation on the precipitate, washing by using deionized water, recrystallizing by using methanol, and then placing in a vacuum drying oven at 50 ℃ for drying to obtain 4- (4-carboxyphenoxy) phthalonitrile;
under the protection of nitrogen, dissolving 2g of 4- (4-carboxyphenoxy) phthalonitrile and 0.8g of zinc chloride in 30mL of n-amyl alcohol, heating to 50 ℃, adding 1.6mL of 1, 8-diazabicycloundecen-7-ene, heating to 130 ℃, reacting for 6h, cooling to room temperature, adding hydrochloric acid into the reaction liquid to adjust the pH value to 1, generating a large amount of flocculent precipitates in the reaction liquid, filtering the reaction liquid, washing a filter cake to be neutral by deionized water, drying in vacuum at 50 ℃, and grinding to obtain zinc phthalocyanine powder.
Example 2
Preparation of cobalt phthalocyanine
Under the protection of nitrogen, adding 50mL of dimethyl sulfoxide into a reaction bottle, adding 3g of 4-nitrophthalonitrile and 7g of p-hydroxybenzoic acid under stirring, adding 12g of potassium carbonate, reacting for 24 hours under stirring at 30 ℃, then dropwise adding the reaction solution into 150mL of deionized water, adjusting the pH value to 1 by using concentrated hydrochloric acid, separating out flocculent precipitate, carrying out suction filtration and separation on the precipitate, washing by using deionized water, recrystallizing by using methanol, and then placing in a vacuum drying oven at 50 ℃ for drying to obtain 4- (4-carboxyphenoxy) phthalonitrile;
under the protection of nitrogen, dissolving 2g of 4- (4-carboxyphenoxy) phthalonitrile and 1g of cobalt acetate in 30mL of n-amyl alcohol, heating to 50 ℃, adding 1.6mL of 1, 8-diazabicycloundec-7-ene, heating to 130 ℃, reacting for 6h, cooling to room temperature, adding hydrochloric acid into reaction liquid to adjust the pH value to 1, generating a large amount of flocculent precipitates in the reaction liquid, carrying out suction filtration on the reaction liquid, washing a filter cake to be neutral by deionized water, carrying out vacuum drying at 50 ℃, and grinding to obtain cobalt phthalocyanine powder.
Example 3
Preparation of copper phthalocyanine
Under the protection of nitrogen, adding 50mL of dimethyl sulfoxide into a reaction bottle, adding 4g of 3-nitrophthalonitrile and 7g of p-hydroxybenzoic acid under stirring, adding 14g of potassium carbonate, reacting for 24 hours under stirring at 30 ℃, then dropwise adding the reaction solution into 150mL of deionized water, adjusting the pH value to 1 by using concentrated hydrochloric acid, separating out flocculent precipitate, carrying out suction filtration and separation on the precipitate, washing by using deionized water, recrystallizing by using methanol, and then placing in a vacuum drying oven at 50 ℃ for drying to obtain 4- (4-carboxyphenoxy) phthalonitrile;
under the protection of nitrogen, dissolving 2g of 4- (4-carboxyphenoxy) phthalonitrile and 0.7g of cuprous chloride in 30mL of n-amyl alcohol, heating to 50 ℃, adding 1.6mL of 1, 8-diazabicycloundecen-7-ene, heating to 130 ℃, reacting for 6h, cooling to room temperature, adding hydrochloric acid into the reaction liquid to adjust the pH value to 1, generating a large amount of flocculent precipitates in the reaction liquid, carrying out suction filtration on the reaction liquid, washing a filter cake to be neutral by deionized water, carrying out vacuum drying at 50 ℃, and grinding to obtain copper phthalocyanine powder.
Example 4
S1, adding concentrated sulfuric acid into a reaction bottle, cooling to 5 ℃, adding 10g of graphite and 5g of sodium nitrate, stirring for 30min, adding 20g of potassium permanganate at 10 ℃, keeping the temperature of the reaction solution below 20 ℃, and stirring to react for 1h after the addition to obtain a solution I;
s2, heating the first solution to 30 ℃, stirring and reacting for 0.5h, then adding 100mL of deionized water into the first solution, heating to 95 ℃, continuing to react for 30min, then adding 15mL of hydrogen peroxide solution with the mass fraction of 5% into the first solution, stirring uniformly, filtering, washing the filter cake with deionized water until the filter cake does not contain sulfate ions, and drying the filter cake in a vacuum drying oven for 24h to obtain graphite oxide;
and S3, crushing and grinding the graphite oxide obtained in the step S2, dissolving the graphite oxide in water, performing ultrasonic treatment for 20min, centrifuging at 6000r/min for 20min, taking supernatant, heating to remove excessive moisture, and drying at 60 ℃ for 24h to obtain the graphene oxide.
Example 5
Preparation of organic-inorganic composite nano photocatalyst
2g of zinc phthalocyanine powder obtained in example 1 and 2g of graphene oxide obtained in example 4 were dissolved in chloroform to obtain a zinc phthalocyanine solution of 8mg/mL and a graphene oxide solution of 2mg/mL, respectively, and then the zinc phthalocyanine solution and the graphene oxide solution were mixed in a volume ratio of 1: 0.8, mixing, ultrasonically dispersing for 1h, filtering, concentrating the filtrate under reduced pressure, and drying to obtain a graphene oxide-zinc phthalocyanine compound;
dissolving 0.1g of sodium dodecyl benzene sulfonate in 10mL of deionized water, adding 1g of sodium molybdate, 0.9g of thiourea and 3g of graphene oxide-zinc phthalocyanine compound, ultrasonically dispersing and stirring for 0.5h, then transferring the dispersion liquid into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, sucking out the supernatant in the reaction liquid to obtain bottom fixed powder, washing with the deionized water for 3 times, placing in an oven at 80 ℃ for drying for 16h, and grinding to obtain the organic-inorganic composite nano photocatalyst A.
Example 6
Preparation of organic-inorganic composite nano photocatalyst
2g of cobalt phthalocyanine powder obtained in example 2 and 2g of graphene oxide obtained in example 4 were dissolved in chloroform, respectively, to obtain an 8mg/mL cobalt phthalocyanine solution and a 2mg/mL graphene oxide solution, and then the cobalt phthalocyanine solution and the graphene oxide solution were mixed in a volume ratio of 1: 0.8, mixing, ultrasonically dispersing for 1h, filtering, concentrating the filtrate under reduced pressure, and drying to obtain a graphene oxide-cobalt phthalocyanine compound;
dissolving 0.1g of sodium dodecyl benzene sulfonate in 10mL of deionized water, adding 1g of sodium molybdate, 0.9g of thiourea and 3g of graphene oxide-cobalt phthalocyanine compound, ultrasonically dispersing and stirring for 0.5h, then transferring the dispersion liquid into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, sucking out the supernatant in the reaction liquid to obtain bottom fixed powder, washing with the deionized water for 3 times, placing in an oven at 80 ℃, drying for 16h, and grinding to obtain the organic-inorganic composite nano photocatalyst B.
Example 7
Preparation of organic-inorganic composite nano photocatalyst
2g of copper phthalocyanine powder obtained in example 3 and 2g of graphene oxide obtained in example 4 were dissolved in chloroform to obtain a copper phthalocyanine solution of 8mg/mL and a graphene oxide solution of 2mg/mL, respectively, and then the copper phthalocyanine solution and the graphene oxide solution were mixed in a volume ratio of 1: 0.8, mixing, ultrasonically dispersing for 1h, filtering, concentrating the filtrate under reduced pressure, and drying to obtain a graphene oxide-copper phthalocyanine compound;
dissolving 0.1g of sodium dodecyl benzene sulfonate in 10mL of deionized water, adding 1g of sodium molybdate, 0.9g of thiourea and 3g of graphene oxide-copper phthalocyanine compound, ultrasonically dispersing and stirring for 0.5h, then transferring the dispersion liquid into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, sucking out the supernatant in the reaction liquid to obtain bottom fixed powder, washing with the deionized water for 3 times, placing in an oven at 80 ℃ for drying for 16h, and grinding to obtain the organic-inorganic composite nano photocatalyst C.
Comparative example 1
2g of zinc phthalocyanine powder obtained in example 1 and 2g of graphene oxide obtained in example 4 were dissolved in chloroform to obtain a zinc phthalocyanine solution of 8mg/mL and a graphene oxide solution of 2mg/mL, respectively, and then the zinc phthalocyanine solution and the graphene oxide solution were mixed in a volume ratio of 1: 0.8, mixing, ultrasonically dispersing for 1h, filtering, concentrating the filtrate under reduced pressure, and drying to obtain the graphene oxide-zinc phthalocyanine compound, wherein the graphene oxide-zinc phthalocyanine compound is used as the photocatalyst D.
Comparative example 2
Dissolving 0.1g of sodium dodecyl benzene sulfonate in 10mL of deionized water, adding 1g of sodium molybdate, 0.9g of thiourea and 2g of zinc phthalocyanine, ultrasonically dispersing and stirring for 0.5h, then transferring the dispersion liquid into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, sucking out the supernatant in the reaction liquid to obtain bottom fixed powder, washing with the deionized water for 3 times, drying in an oven at 80 ℃ for 16h, and grinding to obtain the composite nano photocatalyst E.
Example 8
The photocatalytic hydrogen production activity experiment is carried out at 25 ℃ in a 100mL pyrex reactor, and 50mL of the hydrogen production catalyst with the volume ratio of 1: 4, after blowing nitrogen gas into the solution and removing oxygen gas by vacuum, 25mg of the photocatalysts obtained in examples 5, 6 and 7 and comparative examples 1 and 2 were dispersed in the mixed solution, and the mixed solution was continuously irradiated for 4 hours using a 300W xenon lamp equipped with an optical cutoff filter of 420nm to decompose the mixed solution to generate hydrogen gas, and the generated hydrogen gas was quantified using a Shimazu GC2010 gas chromatograph, and the results were as shown in the following table:
the above table shows that the photocatalyst A, B, C prepared by the method has good catalytic performance, and the hydrogen production rate is about 2.2mmol/h, while the photocatalyst D is a binary compound of zinc phthalocyanine and graphene, and the hydrogen production rate is obviously lower than A, B, C, which indicates that the photocatalytic activity of the ternary compound photocatalyst of molybdenum disulfide, graphene and metal phthalocyanine is higher than that of the binary photocatalyst, and the photocatalyst E is a binary compound photocatalyst of zinc phthalocyanine and molybdenum disulfide, and the hydrogen production efficiency is obviously lower than that of A, B, C, which indicates that the graphene plays a role in increasing the specific surface area of the catalyst, and the catalytic efficiency is effectively increased.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. A preparation method of an organic-inorganic composite nano photocatalyst is characterized by comprising the following steps:
(1) under the protection of nitrogen, adding dimethyl sulfoxide into a reaction bottle, adding nitro-substituted phthalonitrile, p-hydroxybenzoic acid and potassium carbonate under stirring, stirring and reacting for 20-30h at 25-35 ℃, dropwise adding the reaction liquid into deionized water, adjusting the pH value to 1 by using concentrated hydrochloric acid, and obtaining a phthalonitrile intermediate after suction filtration, washing and drying;
(2) under the protection of nitrogen, the phthalonitrile intermediate obtained in the step (1) and MXnDissolving in n-amyl alcohol, heating to 40-50 ℃, adding 1, 8-diazabicycloundec-7-ene, heating to 100 ℃ and 130 ℃ for reaction for 4-6h, adding hydrochloric acid into the reaction solution to adjust the pH value to 1-3, and obtaining metal phthalocyanine powder after suction filtration, washing, drying and grinding;
(3) respectively dissolving the metal phthalocyanine powder and graphene oxide obtained in the step (2) in chloroform to obtain a metal phthalocyanine solution and a graphene oxide solution, and then mixing the metal phthalocyanine solution and the graphene oxide solution according to a volume ratio of 1: 0.5-1, ultrasonically dispersing for 0.5-2h, filtering, concentrating under reduced pressure, and drying to obtain graphene oxide-metal phthalocyanine compound;
(4) and (2) dissolving sodium dodecyl benzene sulfonate in deionized water, adding sodium molybdate, thiourea and the graphene oxide-metal phthalocyanine compound obtained in the step (3), ultrasonically dispersing and stirring for 0.5-1h, transferring the dispersion liquid into a high-pressure reaction kettle, reacting for 20-30h at the temperature of 180-220 ℃, sucking out the supernatant in the reaction liquid to obtain bottom fixed powder, washing for 3 times by using the deionized water, and drying in an oven at the temperature of 80-90 ℃ for 10-16h to obtain the organic-inorganic composite nano photocatalyst.
2. The method for preparing an organic-inorganic composite nano photocatalyst as claimed in claim 1, wherein the molar ratio of 4-nitrophthalonitrile, p-hydroxybenzoic acid and potassium carbonate in step (1) is 1: 2-3:2-4, adding 10-20mL of dimethyl sulfoxide into each gram of 4-nitrophthalonitrile.
3. The method for preparing an organic-inorganic composite nano-photocatalyst as claimed in claim 1, wherein said MX in step (1)nIs selected from one of ferrous chloride, cobalt chloride, copper chloride, cuprous chloride, zinc chloride, nickel acetate and cobalt acetate, and the nitro-substituted phthalonitrile is 3-nitrophthalonitrile or 4-nitrophthalonitrile.
4. The method for preparing an organic-inorganic composite nano photocatalyst as claimed in claim 1, wherein the molar ratio of the phthalonitrile intermediate to the metal chloride in step (2) is 1: 2-4, 10-20mL of n-pentanol and 1-2mL of 1, 8-diazabicycloundecen-7-ene are added per gram of phthalonitrile intermediate.
5. The method according to claim 1, wherein the concentration of the metal phthalocyanine solution in step (3) is 8-10mg/mL, and the concentration of the graphene oxide solution is 2-4 mg/mL.
6. The method for preparing an organic-inorganic composite nano photocatalyst according to claim 1, wherein the method for preparing graphene oxide in step (3) comprises:
s1, adding concentrated sulfuric acid into a reaction bottle, cooling to 0-5 ℃, adding graphite and sodium nitrate, stirring for 20-40min, adding potassium permanganate at 10-20 ℃, and stirring to react for 1-2h after the addition is finished to obtain a first solution;
s2, heating the first solution to 30-40 ℃, stirring and reacting for 0.5-1h, then adding deionized water into the first solution, heating to 90-100 ℃, continuing to react for 20-40min, then adding a hydrogen peroxide solution with the mass fraction of 5% into the first solution, stirring uniformly, and filtering to obtain graphite oxide;
s3, crushing and grinding the graphite oxide obtained in the step S2, dissolving the graphite oxide in water, performing ultrasonic treatment for 10-20min, centrifuging for 10-20min at 6000-7000r/min, taking supernatant, heating to remove excessive moisture, and drying at 60 ℃ for 20-40h to obtain the graphene oxide.
7. The method for preparing an organic-inorganic composite nano photocatalyst according to claim 6, wherein in S1, the mass ratio of graphite to sodium nitrate to potassium permanganate is 1: 0.4-0.6: 2-4, 20-30mL of concentrated sulfuric acid is used per gram of graphite, 20-30mL of deionized water and 2-3mL of hydrogen peroxide solution are added per gram of graphite in S2, and 80-150mL of deionized water is used per gram of graphite oxide in S3.
8. The method for preparing an organic-inorganic composite nano photocatalyst according to claim 1, wherein the mass ratio of the sodium molybdate, the thiourea, the sodium dodecyl benzene sulfonate and the graphene oxide-metal phthalocyanine composite in the step (4) is 1: 0.8-1.2: 0.1-0.3: 2-5.
9. An organic-inorganic composite nano-photocatalyst, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
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| CN115254193A (en) * | 2022-08-15 | 2022-11-01 | 中南大学 | Palladium phthalocyanine molecular catalyst, preparation method of carbon substrate supported palladium phthalocyanine molecular catalyst and application of catalyst |
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| CN113019401A (en) * | 2021-03-11 | 2021-06-25 | 黑龙江工业学院 | Preparation method, application and application method of graphene-based photocatalytic composite material |
| CN113019401B (en) * | 2021-03-11 | 2021-09-24 | 黑龙江工业学院 | Preparation method, application and application method of graphene-based photocatalytic composite material |
| CN115254193A (en) * | 2022-08-15 | 2022-11-01 | 中南大学 | Palladium phthalocyanine molecular catalyst, preparation method of carbon substrate supported palladium phthalocyanine molecular catalyst and application of catalyst |
| CN115254193B (en) * | 2022-08-15 | 2023-11-03 | 中南大学 | Palladium phthalocyanine molecular catalyst, preparation method and application of palladium phthalocyanine molecular catalyst supported by carbon substrate |
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