CN110449187A - A kind of preparation method and application of perovskite-metal complex composite material - Google Patents
A kind of preparation method and application of perovskite-metal complex composite material Download PDFInfo
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- CN110449187A CN110449187A CN201910675289.XA CN201910675289A CN110449187A CN 110449187 A CN110449187 A CN 110449187A CN 201910675289 A CN201910675289 A CN 201910675289A CN 110449187 A CN110449187 A CN 110449187A
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 40
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910019142 PO4 Chemical group 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 239000010452 phosphate Chemical group 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000003960 organic solvent Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000012296 anti-solvent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000013065 commercial product Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 229910020598 Co Fe Inorganic materials 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000012074 organic phase Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 31
- 150000002367 halogens Chemical class 0.000 abstract description 30
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- -1 phosphate Metal complex Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BFSPAPKTIGPYOV-BQYQJAHWSA-N (e)-1-[4-(4-hydroxyphenyl)piperazin-1-yl]-3-thiophen-2-ylprop-2-en-1-one Chemical compound C1=CC(O)=CC=C1N1CCN(C(=O)\C=C\C=2SC=CC=2)CC1 BFSPAPKTIGPYOV-BQYQJAHWSA-N 0.000 description 1
- CMNUYDSETOTBDE-UHFFFAOYSA-N 1-benzyl-4h-pyridine-3-carboxamide Chemical compound C1=CCC(C(=O)N)=CN1CC1=CC=CC=C1 CMNUYDSETOTBDE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FITZJYAVATZPMJ-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 FITZJYAVATZPMJ-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of halogen perovskite material ABX3With the preparation method and application of the metal complex M complex composite material constructed.Composite material is synthesized by two methods: 1) by the halogen perovskite material ABX of pre-synthesis3It is added in the solution of the metal complex of the functional groups such as carboxyl, amino or phosphate, using the coordination between the functional group and halogen perovskite material of metal complex, forms composite material under certain conditions；2) metal complex of function dough is added in halogen perovskite material preparation process, forms composite material in halogen perovskite surface in situ adsorbent complex.Synthetic method of the invention is convenient, can operate under favorable reproducibility, room temperature；Resulting composite material can be applied to photocatalysis CO simultaneously2Reduction, and Photocatalyzed Hydrogen Production, organic matter degradation can be further used for etc. and light/photoelectrocatalysis field.
Description
Technical field
The invention belongs to the preparation of advanced composite material (ACM) and application fields, and in particular to a kind of structure is ABX3Halogen calcium
The preparation method and application for the composite material that titanium ore material and metal complex are constructed.
Background technique
Halogen perovskite material is since big with extinction coefficient, light absorption range is wide, carrier diffusion length is long, band gap is adjustable
The advantages that saving, being easily-synthesized is developed very rapidly in recent years, is led in solar cell, photodetector, luminescent device, photocatalysis etc.
Domain all presents vast potential for future development.Particularly, the good visible light absorption capacity of halogen perovskite material, suitable energy band
Position makes it show good development potentiality in terms of photocatalysis, currently reported to be applied to photocatalysis hydrogen production, CO2
Reduction, degradating organic dye etc..But halogen perovskite still exist as photochemical catalyst photogenerated charge it is compound it is serious,
Catalytic reaction kinetics slow problem still needs to be further increased in catalytic activity and selectivity of product.
The available strategy for improving semiconductor catalyst photocatalysis performance is to construct compound heterogenous catalyst.Select appropriate band
The material of structure constructs composite catalyst, can not only provide effective charge transferring channel and inhibit answering for photo-generate electron-hole
The function of closing to promote the separation of charge, and can integrate different component obtains the catalytic performance of enhancing.It has reported at present
Semiconductors coupling catalyst mainly include semiconductor/metal nano-particles reinforcement catalyst, semiconductor/semiconductor composite catalyzing
Agent, semiconductor/metal organic frame composite catalyst and semiconductor/metal compound composite catalyst etc..Wherein, metal combination
Object is common a kind of efficient molecular catalyst in photocatalysis and electrocatalytic reduction, product selection good with catalytic activity
The features such as property is high.It is prepared into composite catalyst with semiconductors coupling, not only can effectively solve metal complex in homogeneous catalysis
The problem of being easy to happen aggregation in system and inactivating, and the catalytic activity and selectivity of product of composite material can be effectively improved.
It has been reported that metal complex and TiO2、CdS、g-C3N4Equal semiconductor materials are compound constructs Heterogeneous Composite catalyst, obtain
Higher CO2Reducing property.It constructs metal complex and halogen perovskite material are compound novel heterogenous catalyst and is then expected to
The catalytic activity and selectivity of product that promote the separation of charge efficiency of perovskite material and integrated complex obtain the catalysis of enhancing
Performance is not yet exploited at present.
Therefore, how by metal complex and halogen perovskite material it is compound prepare effective catalyst and probe into its property tool
There is important meaning, and the difficulty that urgently one of ordinary skill in the art capture.
Summary of the invention
The problems such as there are photogenerated charge low separation efficiencies, poor catalytic activity due to existing halogen perovskite material, this hair
Bright purpose is to provide a kind of halogen perovskite ABX3The preparation method for the composite material that material and metal complex are constructed, it is compound
The synthetic method of material is simple to operate and friendly to environment, reproducibility is high and can operate in normal temperature air atmosphere.
It is a further object of the present invention to provide a kind of preparations by above-mentioned halogen perovskite-metal complex composite material
The perovskite of halogen obtained by method-application of the metal complex composite material in photocatalysis field.
The present invention is realized by following technical solution.
Perovskite-metal complex composite material preparation method one, comprising the following steps:
1) preparation of halogen perovskite material:
The halogen perovskite material can be commercial product or by anti-solvent method, cooling crystallization method, hot injection method etc.
Synthesis technology is made；
The concrete technology of the anti-solvent method is:
The precursor solution of A and the precursor solution of B are prepared respectively, and the precursor solution of A is added to perovskite material
Poor solvent in, be added with stirring the precursor solution of B, obtain halogen perovskite material ABX3；By product centrifuge washing point
From.
The concrete technology of the cooling crystallization method is:
By excessive AX and BX2HX/H is made an addition to according to molar ratio 1:13PO2In aqueous solution, increases temperature and makes it completely dissolved,
Being cooled to room temperature makes ABX3It is precipitated, centrifuge separation is dried to obtain halogen perovskite ABX3Material.
2) preparation of metal complex M complex:
Metal complex M complex (the M=Re Co Fe Ni Mn Mo W Ru Os Rh Ir Pd Cr Cu
Deng) be commercial product or by organic synthesis technique be made, the metal complex includes but is not limited to carboxyl, phosphate, ammonia
The complex of the functional groups such as base, the metal complex can be polypyridine class complex, thio-alcohol complex, azepine
The complex of ring arbine complex or other forms.
3) halogen perovskite-metal complex composite material preparation:
It disperses the halogen perovskite material synthesized in step 1) in organic solvent, certain volume is added thereto
The metal complex solution of 20-60% stirs under room temperature；Reaction product is centrifugated, is cleaned with organic solvent.
Further, in step 1), the A in the precursor solution and AX of the A is Cs+、MA+、FA+Equal monovalent cations
One of or it is a variety of；The precursor solution and BX of B2In B can be Pb2+、Sn2+Deng；AX,BX2In X be Cl-、Br-、I-
One of or a variety of mixing.
Further, in step 3), the organic solvent for dispersing halogen perovskite material can be toluene, chlorine
Benzene, ethyl acetate etc..
Further, in step 3), the metal complex solution of addition and the volume ratio of halogen perovskite dispersion liquid are about
Between 1:100-1:1.
Further, in step 3), the time stirred under room temperature between 5-15h, preferably 12h；Product is with organic molten
The number of agent cleaning is between 2-4 times, and preferably 3 times.
Perovskite-metal complex composite material preparation method two, comprising the following steps:
1) preparation of metal complex M complex:
Metal complex M complex (the M=Re Co Fe Ni Mn Mo W Ru Os Rh Ir Pd Cr Cu
Deng) be commercial product or by organic synthesis technique be made, the metal complex includes but is not limited to carboxyl, phosphate, ammonia
The complex of the functional groups such as base, the metal complex can be polypyridine class complex, thio-alcohol complex, azepine
The complex of ring arbine complex or other forms.
2) halogen perovskite-metal complex composite material preparation:
By AX, BX21:1 is dissolved in organic solvent in molar ratio, and oleic acid is added thereto (with above-mentioned liquor capacity ratio
Perovskite precursor solution is prepared for 0-1:6), oleyl amine (being 0-1:20 with above-mentioned liquor capacity ratio), 0.5- is added thereto
20% metal complex stirs under room temperature；The solution being previously formed is S1, according to S1: the volume ratio of poor solvent is 1:10
S1 is added in poor solvent solution~80 ratio, and reaction solution is centrifugally separating to obtain product.
Further, in step 2), the A in the AX can be Cs+、MA+、FA+One of equal monovalent cations are more
Kind；BX2In B can be Pb2+、Sn2+、Pd2+Deng；AX,BX2In X be Cl-、Br-、I-One of or a variety of mixing.
Further, in step 2), the organic solvent can be DMF, acetonitrile etc..
Further, in step 2), S1: the volume ratio of poor solvent is 1:10~80.
Further, in step 2), poor solvent can be toluene, chloroform etc..
Resulting perovskite-metal complex the composite material of the present invention is with CsPbBr3-Re(CO)3Br (dcbpy) is representative,
It can be used for efficient catalytic CO2Reduction reaction.Such composite material can also be used for Photocatalyzed Hydrogen Production, photocatalytically degradating organic dye etc.
The research fields such as photocatalysis and photoelectrocatalysis.
The application of the perovskite of the embodiment of the present invention-metal complex composite material, can be expressed as follows:
Solvent, a small amount of sacrifice reagent and catalyst are added in sealed glass jars, then seals vial, and taken out
The air in bottle is removed in vacuum, is then charged with the CO of sufficient amount2Gas carries out catalysis reaction under illumination, with gas chromatograph into
Row product detection.
Further, the solvent can be the organic solvents such as toluene, ethyl acetate, acetonitrile, be saturated HI, HBr aqueous solution
Deng；Reaction dissolvent includes but is not limited to that organic solvent is used alone, and saturated aqueous solution is used alone, or by organic solvent and water
Solution carries out a certain proportion of mixing.
Further, sacrificing reagent can be isopropanol, BIH, BNAH, triethanolamine, three ethyl alcohol etc..
By above-mentioned technical proposal, the invention has the following advantages:
1) present invention has constructed a kind of novel perovskite-metal complex composite material, and synthesis process is simple, material weight
Existing property is good, can synthesize under room temperature.
2) the resulting perovskite-metal complex composite material of the present invention can be used for photocatalysis CO2Reduction reaction, can also be into
One step is for other photocatalytic applications fields and electro-catalysis, photoelectrocatalysis field such as Photocatalyzed Hydrogen Production, degradating organic dyes.
In order to better understand and implement, the present invention will be described in detail with specific preferred embodiment with reference to the accompanying drawing.
Detailed description of the invention
Fig. 1 is the CsPbBr in the embodiment of the present invention 13-Re(CO)3The XRD diagram of Br (dcbpy) composite material.
Fig. 2 is the CsPbBr in the embodiment of the present invention 13-Re(CO)3The TEM of Br (dcbpy) composite material schemes.
Fig. 3 is the MAPbI in the embodiment of the present invention 33And MAPbI3-Re(CO)3The XRD diagram of Br (dcbpy) composite material.
Fig. 4 is the CsPbBr in the embodiment of the present invention 13-Re(CO)3Br (dcbpy) composite material and CsPbBr3, photocatalysis
Restore CO2The SE yield figure of continuous 3h.
Specific embodiment
It is of the invention to reach the technological means and its technological achievement that predetermined goal of the invention is taken further to illustrate, with
Lower with specific embodiments and the drawings is illustrated halogen perovskite-metal complex composite material of the present invention.
The invention discloses a kind of halogen perovskite material ABX3(A=Cs+、MA+、FA+One of equal monovalent cations
Or a variety of mixing；B=Pb2+、Sn2+Deng；X=Cl-、Br-、I-Or its a variety of mixing) and metal complex M complex (M=Re
Co Fe Ni Mn Mo W Ru Os Rh Ir Pd Cr Cu etc.) preparation method and application of composite material that construct.The present invention
Using the method for adsorption by halogen perovskite ABX3Material carries out compound with metal complex M complex.Composite material
It can be synthesized by two methods:
1) by the halogen perovskite material ABX of pre-synthesis3It has been added to the functional groups such as carboxyl, amino or phosphate
Metal complex solution in, utilize the coordination between the functional group and halogen perovskite material of metal complex, In
Composite material is formed under conditions of certain；
2) metal complex of function dough is added in halogen perovskite material preparation process, on halogen perovskite surface
Adsorbent complex in situ forms composite material.Synthetic method of the invention is convenient, can operate under favorable reproducibility, room temperature；Institute simultaneously
The composite material obtained can be applied to photocatalysis CO2Reduction, and Photocatalyzed Hydrogen Production, organic matter degradation can be further used for etc. and light/
Photoelectrocatalysis field.
Embodiment 1
A kind of preparation method of perovskite-metal complex composite material, comprising the following steps:
Step 1, by 0.440g Cs2CO3It is dissolved in 3mL propionic acid and obtains the precursor solution of caesium；By 0.550g PbBr2Add
Enter and obtains the precursor solution of lead into the mixed solution of 1mL isopropanol, 1mL propionic acid and 1mL butylamine.Before taking 10 μ L propionic acid caesiums
It drives liquid solution to be diluted in the mixed solution of 1mL n-hexane and 0.5mL isopropanol, the PbBr of 50 μ L is rapidly joined under stirring2's
Precursor solution has glassy yellow CsPbBr3Nanocrystalline generation.2min separation product, again with toluene are centrifuged under the revolving speed of 8000rpm
It is cleaned；
Step 2, the Re (CO) of 0.2g5The 4,4- dicarboxylic acids bipyridyl (dcbpy) of Br and 0.1g is dissolved in the toluene of 15mL
In solution, N2The lower 115 DEG C of back flow reaction 15h of atmosphere；Reaction is centrifugated after being cooled to room temperature, then successively with methylene chloride and
Methanol cleaning, finally revolving obtains Re (CO)3Br (dcbpy) complex powder；
Step 3, by 5mg Re (CO) obtained in step 23The ethyl acetate that Br (dcbpy) complex is dissolved in 10mL is molten
In liquid；The CsPbBr that step 1 is synthesized3It is nanocrystalline to be scattered in the ethyl acetate solution of 5mL, 300 μ are then added thereto again
The Re (CO) of L312h is stirred under the ethyl acetate solution room temperature of Br (dcbpy) complex, after reaction solution is centrifugated, product
It is cleaned 3 times with ethyl acetate.
It as shown in figure 1 and 2, is the resulting CsPbBr of the present embodiment3-Re(CO)3The XRD diagram of Br (dcbpy) composite material
Scheme with TEM, it can be seen that composite material does not destroy CsPbBr3Nanocrystalline structure.
Embodiment 2
A kind of perovskite-metal complex composite material CsPbBr1.5I1.5-Re(CO)3The preparation method of Br (dpbpy),
The following steps are included:
Step 1, by 0.440g Cs2CO3It is dissolved in 3mL propionic acid and obtains the precursor solution of caesium；By 0.2750g PbBr2With
0.3458g PbI2It is added in the mixed solution of 1mL isopropanol, 1mL propionic acid and 1mL butylamine and obtains the precursor solution of lead.It takes
The precursor solution of 10 μ L propionic acid caesiums is diluted in the mixed solution of 1mL n-hexane and 0.5mL isopropanol, is rapidly joined under stirring
The PbI of 50 μ L2Precursor solution, have red CsPbBr1.5I1.5Nanocrystalline generation.2min is centrifuged under the revolving speed of 8000rpm
Separation product, then cleaned with ethyl acetate；
Step 2, the Re (CO) of 0.2g52,2'- bipyridyl -4,4'- the bis phosphoric acid of Br and 0.1g is dissolved in the toluene of 15mL
In solution, N2The lower 115 DEG C of back flow reaction 15h of atmosphere.Reaction is centrifugated after being cooled to room temperature, then successively with methylene chloride and
Methanol cleaning, finally revolving obtains Re (CO)3Br (dpbpy) complex powder；
Step 3, by 3mg Re (CO) obtained in step 23The ethyl acetate that Br (dpbpy) complex is dissolved in 10mL is molten
In liquid.
The CsPbBr that step 1 synthesizes1.5I1.5It is nanocrystalline to be scattered in the ethyl acetate solution of 5mL, then add thereto again
Enter the Re (CO) of 1000 μ L312h is stirred under the ethyl acetate solution room temperature of Br (dpbpy) complex, reaction solution is centrifugated
Afterwards, product cleans 3 times with ethyl acetate to get CsPbBr1.5I1.5-Re(CO)3Br (dpbpy) composite material.
Embodiment 3
A kind of perovskite-metal complex composite material MAPbI3-Re(CO)3The preparation method of Br (dcbpy), including with
Lower step:
By 0.5gMAI, 1.5gPbI2It is dissolved in 3mL DMF, and 300 μ L oleic acid, 60 μ L oleyl amines, Xiang Rong is added thereto
The Re (CO) of 3mg is added in liquid3Br (dcbpy) complex powder stirs 10h under room temperature；The solution being previously formed is S1, according to
S1: S1 is added in chloroform the ratio that the volume ratio of poor solvent is 1:60, and reaction solution is centrifugally separating to obtain product.
Attached drawing 3 is the resulting MAPbI of the present embodiment3-Re(CO)3The XRD diagram of Br (dcbpy) composite material, it can be seen that multiple
Condensation material does not destroy MAPbI3Structure.
Embodiment 4
A kind of perovskite-metal complex composite material MAFAPbI3-Mn(bpy)(CO)3The preparation method of Br, including with
Lower step:
Step 1, by 58.8mg2,2'- bipyridyl and 99.8mg Mn (CO)5Br is dissolved in 40mL ether, and dark-state is next time
Flow 3h.Mn (bpy) (CO) is obtained by filtration3Br orange powder, is washed with ether, vacuum drying.
Step 2, by 1g PbI2, 0.5g FAI, 0.1g MAI be dissolved in 3ml DMF, and 300 μ L oil be added thereto
The Mn (bpy) (CO) of 5mg is added into solution for acid, 60 μ L oleyl amines3Br complex powder stirs 10h under room temperature；It is previously formed
Solution be S1, according to S1: the volume ratio of poor solvent be 1:60 ratio by S1 be added chloroform in, reaction solution is centrifuged
Isolated composite material MAFAPbI3-Mn(bpy)(CO)3Br。
Application test example 1
By the perovskite of embodiment 1-metal complex composite material in photo catalytic reduction CO2Application, including following step
It is rapid:
1) 9mL toluene, 1mL isopropanol (sacrificing reagent) and CsPbBr are added in 40mL sealed glass jars3-Re(CO)3Br
(dcbpy) then composite catalyst seals vial, and carry out vacuumizing the air removed in bottle, is then charged with sufficient amount
CO2Gas.
2) light source tested using the xenon lamp of 150W as photocatalysis, in AM1.5G, 420nm optical filter and 150mW cm-2
Light intensity under carry out photocatalysis test, and using gas chromatograph progress gaseous product analysis.
Photocatalysis test result is shown, with individual CsPbBr3It compares, CsPbBr3-Re(CO)3Br (dcbpy) composite wood
Expect photo catalytic reduction CO2Activity it is higher, as shown in Fig. 4.
Application test example 2
Utilize CsPbBr prepared by embodiment 13Nanocrystalline, Re (CO)3Br (dcbpy) complex is raw material, preparation
The composite material of different content metal complex.Specific steps are as follows:
By 5mg Re (CO) obtained in 1 step 2 of embodiment3Br (dcbpy) complex is dissolved in the ethyl acetate of 10mL
In solution.The CsPbBr that step 1 synthesizes3It is nanocrystalline to be scattered in the ethyl acetate solution of 5mL, 100 μ are then added thereto again
The Re (CO) of L312h is stirred under the ethyl acetate solution room temperature of Br (dcbpy) complex, after reaction solution is centrifugated, product
It is cleaned 3 times with ethyl acetate.
Application test example 3
Utilize CsPbBr prepared by embodiment 13Nanocrystalline, Re (CO)3Br (dcbpy) complex is raw material, preparation
The composite material of different content metal complex.Specific steps are as follows:
By 5mg Re (CO) obtained in 1 step 2 of embodiment3Br (dcbpy) complex is dissolved in the ethyl acetate of 10mL
In solution.The CsPbBr that step 1 synthesizes3It is nanocrystalline to be scattered in the ethyl acetate solution of 5mL, then it is added 1000 thereto again
The Re (CO) of μ L312h is stirred under the ethyl acetate solution room temperature of Br (dcbpy) complex, after reaction solution is centrifugated, product
It is cleaned 3 times with ethyl acetate.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, therefore
Without departing from the technical solutions of the present invention, to the above embodiments according to the technical essence of the invention any simply to repair
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of perovskite-metal complex composite material preparation method, which comprises the following steps:
In organic solvent by the metal complex dissolution of 20-60%；Perovskite material is dissolved in organic solvent of the same race, with
The organic solvent solution of the metal complex of 1-10% is added into perovskite material again afterwards, stirs the regular hour under room temperature；
After reaction solution is centrifugated, product is cleaned with organic solvent；
The organic solvent can be in polarity weaker organic solvent such as ethyl acetate, and it is stronger organic molten to be also possible to polarity
In agent such as acetonitrile, DMF, DMSO；
The time stirred under the room temperature can be between 5-15h；The number that the product is cleaned with organic solvent takes second place in 2-4
Between.
2. perovskite as described in claim 1-metal complex composite material preparation method, it is characterised in that:
The time stirred under the room temperature is 12h；The product is 3 times with the number that organic solvent cleans.
3. a kind of perovskite-metal complex composite material preparation method, which comprises the following steps:
In organic solvent by the metal complex dissolution of 1-5%；0-500 is dispersed by the perovskite material synthesized in step 1)
In μ L oleic acid, 0-100 μ L oleyl amine, the organic solvent solution of the metal complex of 1-5% is then added into perovskite material again,
It is stirred under room temperature；The solution being previously formed is S1, according to S1: the volume ratio of poor solvent is that S1 is added the ratio of 1:10~80
In poor solvent solution, reaction solution is centrifugally separating to obtain product.
4. perovskite as claimed in claim 3-metal complex composite material preparation method, it is characterised in that:
The organic solvent can be DMF, DMSO, acetonitrile isopolarity solvent；Oleic acid content for dispersing perovskite material is
100-500μL；The oleyl amine content is 10-100 μ L；S1: the volume ratio of poor solvent is 1:10~80；Poor solvent can be
The poor solvent of the perovskite materials such as chloroform.
5. perovskite as claimed in claim 1 or 3-metal complex composite material preparation method, it is characterised in that:
The perovskite material can be commercial product or by synthesis technologies such as anti-solvent method, hot injection method, cooling crystallization methods
It is made；
1) concrete technology of the anti-solvent method is:
The precursor solution of A and the precursor solution of B are prepared respectively, and the precursor solution of A is added to the good of perovskite material
In solvent, it is added with stirring the precursor solution of B, obtains perovskite material ABX3；Product is centrifugated, and uses organic solvent
It is purified；
2) concrete technology of the cooling crystallization method is:
By AX and BX2It is dissolved in HX solution according to certain molar ratio, increasing temperature makes AX and BX2It is dissolved completely in HX solution
In, being cooled to room temperature makes ABX3It is precipitated, centrifuge separation, vacuum drying obtains perovskite ABX3Material.
6. perovskite as claimed in claim 5-metal complex composite material preparation method, it is characterised in that:
In the concrete technology of the anti-solvent method, in the precursor solution of the A, one of A Cs, MA, FA, Rb, K etc. or
A variety of solution can be carbonate solution, nitrate solution, sulfate liquor etc.；B in the precursor solution of B is B=Pb+,
Sn+,Pd+Deng；X in the precursor solution of B is one of Cl, Br, I or a variety of mixing.
7. perovskite as claimed in claim 1 or 3-metal complex composite material preparation method, it is characterised in that:
The metal complex M complex (M=Re Co Fe Ni Mn Mo W Ru Os Rh Ir Pd Cr Cu etc.) is
Commercial product is made by organic synthesis technique, and the metal complex includes but is not limited to the bases such as carboxyl, phosphate, amino
The complex of group's function dough, the metal complex can be polypyridine class complex, thio-alcohol complex, N-heterocyclic carbine
The complex of complex or other forms.
8. a kind of application of perovskite-metal complex composite material, it is characterised in that: the perovskite-metal complex is multiple
Condensation material is made by perovskite of any of claims 1-7-metal complex composite material preparation method
It is standby to obtain, it is used for efficient catalytic CO2Reduction reaction, or it is used for other photocatalytic applications fields such as Photocatalyzed Hydrogen Production, photocatalysis
Degradating organic dye etc. and electro-catalysis, photoelectrocatalysis field.
9. the application of perovskite as claimed in claim 8-metal complex composite material, it is characterised in that: the CO2Reduction
Reaction includes two classes: one kind is to be CO using such composite material in organic phase2Reduction；One kind is sharp in saturated aqueous solution
CO is with such composite material2Reduction.
10. the application of perovskite as claimed in claim 9-metal complex composite material, it is characterised in that:
Organic solvent or saturated aqueous solution, a small amount of sacrifice reagent and catalyst are added in sealed glass jars, then by glass
Bottle sealing, and carry out vacuumizing the air removed in bottle, it is then charged with the CO of sufficient amount2Gas carries out light with gas chromatograph
Catalysis test.
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