CN114790297B - Crystalline reduction-oxidation cluster-based complex and preparation method and application thereof - Google Patents
Crystalline reduction-oxidation cluster-based complex and preparation method and application thereof Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010668 complexation reaction Methods 0.000 title abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 150000002751 molybdenum Chemical class 0.000 claims description 8
- 150000003681 vanadium Chemical class 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004577 artificial photosynthesis Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000003446 ligand Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 238000000634 powder X-ray diffraction Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- B01J35/39—
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
Abstract
The invention discloses a crystal state reduction-oxide cluster base complex and preparation method and application thereof, comprising the following steps: adding organic ligand, metal salt and deionized water into a polytetrafluoroethylene reaction kettle for hydrothermal synthesis. And cooling to room temperature to obtain the reduction-oxidation type cluster-based complex. The complex can also be applied to artificial photosynthesis performance test in a solid-gas reaction mode. The catalytic system is a photocatalytic reaction process of the catalyst in a mixed atmosphere of water vapor and carbon dioxide, can effectively avoid the problem of liquid product separation, and is one of the most possible ways for realizing industrial production application. The reduction-oxidation cluster-based complex as a photocatalyst can effectively catalyze and reduce CO 2 The selectivity to CO is over 99.5 percent, and the cyclicity and the durability are strong. Compared with the traditional photocatalysis test, the method does not need to add extra photosensitizer and sacrificial agent, and has the advantages of environmental protection, simple process and the like.
Description
Technical Field
The invention relates to a complex and a preparation method and application thereof, in particular to a crystalline reduction-oxidation cluster-based complex and a preparation method and application thereof.
Background
Increasingly exhausted non-renewable energy sources and severe greenhouse effect have reached the critical line of sustainable development. Introducing CO 2 Reducing into energy substances (such as CO, CH) 4 Etc.) have been considered to be one of the most effective methods of mitigating the greenhouse effect and closing the carbon cycle. To date, CO 2 The reduction (2) is usually a hydrogenation reaction under high-temperature and high-pressure conditions or a hydrogenation reaction depending on a noble metal catalyst such as Ru or Pt.
In contrast, photocatalytic CO 2 Reduction reaction (CO) 2 RR) and Water Oxidation Reaction (WOR) is a low-cost, environmentally friendly CO 2 And (5) reusing the strategy. However, the half-reaction of WOR is difficult to achieve, and most of the current catalytic systems require the addition of an additional organic sacrificial agent to provide electrons in the reaction. This not only causes potential environmental pollution, but also increases the separation of liquid productsThe separation difficulty. Therefore, CO is designed and synthesized to contain 2 RR and WOR active site photocatalyst to realize artificial photosynthetic complete reaction is an important target.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a crystalline reduction-oxidation cluster-based complex with excellent photocatalytic performance; it is another object of the present invention to provide a method for preparing a crystalline reduction-oxidation cluster-based complex; the invention also aims to provide an application of the crystalline reduction-oxidation cluster-based complex in the field of photocatalysis.
The technical scheme is as follows: the structural formula of the crystalline reduction-oxidation cluster-based complex is as follows: cu 8 Cl[PMo 8 V 6 O 42 ](p-tr 2 Ph) 4 ·8H 2 And O, the reduction unit and the oxidation unit of which are effectively combined and coupled with each other.
The preparation method of the crystalline reduction-oxidation cluster-based complex adopts a one-pot hydrothermal synthesis method and comprises the following steps: sequentially adding p-tr into a polytetrafluoroethylene high-pressure reaction kettle 2 Ph organic ligand 4,4' - (1, 4-phenyl) bis (4H-1, 2, 4-triazole), metal salt and phosphorus source H 3 PO 3 The tetrabutyl ammonium hydroxide aqueous solution and deionized water are mixed uniformly and heated, then cooled to room temperature, washed and dried, and the black spindle crystal is obtained.
The p-tr 2 The Ph ligand structure is as follows:
preferably, the metal salt includes a vanadium salt, a molybdenum salt and a copper salt, the vanadium salt is NH 4 VO 3 、NaVO 3 Or V 2 O 5 The molybdenum salt is Na 2 MoO 4 ·2H 2 O、(NH 4 ) 2 MoO 4 Or H 3 PMo 12 O 40 ·H 2 O, copper salt is CuCl 2 ·2H 2 O; the mass ratio of vanadium salt, copper salt and molybdenum salt in the metal salt is 1; metal salts and organic complexesThe mass ratio of the body is 1.
Preferably, the volume of the reaction solution in the polytetrafluoroethylene high-pressure reaction kettle is selected to be 1/3-2/3.
Preferably, the heating condition is to maintain at 170-180 ℃ for 2.5-3 days.
The crystalline reduction-oxidation cluster-based complex is applied to the field of photocatalysis. And placing the complex serving as a catalyst under carbon dioxide, argon or a mixed gas of carbon dioxide and argon for photocatalytic test.
Preferably, the light source wavelength range in the photocatalytic test is 300-1100nm, and the photocatalytic test shows that carbon dioxide is catalytically reduced into carbon monoxide with the selectivity of 99.5%.
The invention aims to test the artificial photosynthesis performance of the material by synthesizing a crystalline reduction-oxidation cluster-based complex material through in-situ self-assembly. The oxidation site and the reduction site are assembled in a structure, so that the reduction of carbon dioxide can be catalyzed and water oxidation can be completed, and the problem that artificial photosynthesis needs to add extra photosensitizer and organic sacrificial agent in the prior art is solved. Meanwhile, the oxidation site and the reduction site of the complex are connected through single-bridge oxygen, and compared with the situation that the two catalysts with different functions are connected, the complex is more favorable for the rapid transfer of electrons.
In the present invention, individual oxidation sites { PMo } are compared 8 V 6 O 42 }, individual reduction sites CuL, physical mixture of oxidation and reduction sites ({ PMo) 8 V 6 O 42 } + CuL) and ligand p-tr 2 The result of the photocatalytic performance of Ph itself shows that the photocatalytic performance of RO-4 connecting the oxidation site and the reduction site by single-bridge oxygen coordination is optimal.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) synthesizing an oxidation-reduction cluster by a one-pot method, and having simple operation; (2) The photoreduction reaction does not need to add extra sacrificial agents and photosensitizers, so that the method is green and environment-friendly; (3) Catalyst and CO 2 The catalyst is contacted with water vapor, the separation problem is avoided, and the catalyst can be recycled.
Drawings
FIG. 1 is an optical microscope photograph of a reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 2 is the minimal asymmetric unit of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 3 is a structural unit of a reducing cluster in a reduced-oxidized cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 4 is a structural unit of an oxidized cluster in a reduced-oxidized cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 5 is a diagram showing the coordination of a reducing cluster and an oxidizing cluster through a single-bridge oxygen in a reduced-oxidized cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 6 is a three-dimensional structure diagram of a reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 7 is a PXRD pattern of reduced-oxidation cluster-based complex RO-4 synthesized according to Experimental scheme 1;
FIG. 8 is an X-ray photoelectron spectroscopy (XPS) chart of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 9 shows reduced-oxidized cluster-based complexes RO-4 and { PMo ] synthesized according to Experimental protocol 1 8 V 6 O 42 Ultraviolet spectrum and band gap diagram of solid of CuL;
FIG. 10 is a diagram of ultraviolet electron spectroscopy (UPS) of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 11 is a diagram showing an energy band structure of a reduced-oxide cluster-based complex RO-4 synthesized according to Experimental embodiment 1;
FIG. 12 is a Mott-Schottky (Mott-Schottky) plot of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 13 is a graph of transient photocurrent response of a reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 14 is a different atmosphere photocatalytic CO of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1 2 Reducing the performance graph;
FIG. 15 is a light test cycle diagram of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 16 is a graph of the long term test performance of reduced-oxide cluster-based complex RO-4 synthesized according to Experimental protocol 1;
FIG. 17 shows reduced-oxidized cluster-based complexes RO-4 and { PMo ] synthesized according to Experimental protocol 1 8 V 6 O 42 }、CuL、{PMo 8 V 6 O 42 Physical mixture of } + CuL and p-tr 2 Ph is a plot of CO yield over the catalyst.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
(1) Synthesis of reduction-Oxidation Cluster-based Complex (RO-4)
Sequentially adding p-tr into a clean 15mL polytetrafluoroethylene reaction kettle at room temperature 2 A mixed solution of Ph ligand (15mg, 0.07mmol), ammonium metavanadate (15mg, 0.13mmol), copper chloride dihydrate (30mg, 0.18mmol), sodium molybdate dihydrate (50mg, 0.21mmol), phosphorous acid (10mg, 0.12mmol), tetrabutylammonium hydroxide (10% wt aqueous solution, 100. Mu.L), and deionized water (5 mL) was transferred to a 15mL polytetrafluoroethylene autoclave, heated to 180 ℃ for 3 days, and naturally cooled to room temperature. The product was washed with a large amount of deionized water to give black shuttle crystals RO-4 (FIG. 1).
(2) Photophysical characterization of reduction-oxidation cluster-based complexes (RO-4)
Determining the structure of RO-4 by single crystal X-ray diffraction method; determining the purity and the element valence state of the material by using powder X-ray diffraction spectrum (PXRD) and X-ray photoelectron spectroscopy (XPS); the light absorption capacity and band structure of RO-4 were determined using ultraviolet-visible diffuse reflectance, bandgap maps, transient photocurrent response, mott-Schottky (Mott-Schottky), ultraviolet Photoelectron Spectroscopy (UPS).
(3) Electrochemical characterization of reduction-oxidation cluster-based complexes (RO-4)
Grinding 2mg RO-4, adding 990 μ L ethanol and 10 μ L naphthol solution, ultrasonic treating for 30min to obtain suspension, and dripping the suspension onto 1cm × 2cm conductive glass200 μ L, area 1cm 2 . Photocurrent and Mott-Schottky curve tests were performed after the solution was allowed to air dry. The electrolyte was tested as 0.5M Na 2 And (4) SO4 solution. The conductive glass, the carbon rod and the Ag/AgCl electrode are respectively a working electrode, a counter electrode and a reference electrode.
(4) Photocatalytic performance of reduction-oxidation cluster-based complex (RO-4)
5mg of RO-4 is ground and put into a round-bottom quartz crucible with the diameter of 20mm, and then the quartz crucible is put into a 50mL off-line photocatalytic quartz reactor with top irradiation. 200 μ L of deionized water was added to the reactor. Introducing reaction gas (CO) into the reactor 2 Ar or CO 2 And Ar) for 30min to remove air. The product was detected by gas chromatography.
Example 2
The synthesis in this example was essentially the same as in example 1 above, except that the molybdenum salt used in this example was ammonium molybdate (40 mg) instead of sodium molybdate dihydrate.
Example 3
The synthesis in this example was essentially the same as in example 1 above, except that the molybdenum salt used in this example was phosphomolybdic acid (50 mg) instead of sodium molybdate dihydrate (50mg, 0.21mmol), without the addition of phosphorous acid, which is a source of phosphorus.
Example 4
The synthesis in this example was essentially the same as in example 1 above, except that the vanadium salt used in this example was sodium metavanadate (16 mg) instead of ammonium metavanadate.
By single crystal X-ray diffraction analysis, RO-4 was analyzed from the reduced cluster { Cu } 8 And oxidized clusters { PMo } 8 V 6 O 42 And the bonds are connected through coordination bonds. As shown in FIG. 2, the minimum asymmetric unit of the structure includes 1/2 of the { PMo } 8 V 6 O 42 4 Cu + 1, cl - 1, p-tr 2 A Ph ligand and 1 coordinated water molecule. FIG. 3 shows a reduced cluster { Cu } 8 Structure of 8 Cu + And 8 p-tr 2 Ph ligand bound, four Cu centers + Removing and p-tr 2 Ph ligand is linked to 1 mu 4 -Cl coordination. FIG. 4 shows oxidized clusters { PMo } 8 V 6 O 42 Structural drawing of { PO } center 4 4 (Mo) tetrahedrons 2 VO 13 Cluster, two simultaneous { VO } 5 Are coordinated on both sides of the structure, respectively. As shown in FIG. 5, { Cu 8 Cu in and { PMo } 8 V 6 O 42 The terminal oxygens of { PMo } are connected by coordination bonds, each { PMo 8 V 6 O 42 And four { Cu } 8 Are connected. As shown in FIG. 6, { Cu 8 With the ligand p-tr 2 Ph coordinates to obtain AB-stacking two-dimensional plane structure, RO-4 is oxidation cluster { PMo 8 V 6 O 42 Connecting different layers of Cu through single-bridge oxygen 8 Cluster obtained three-dimensional framework material.
Comparing the measured PXRD pattern of the RO-4 material with the simulated PXRD pattern, as shown in FIG. 7, the RO-4 obtained from the experiment has good consistency with the simulated curve, which proves that the material purity is very high. As shown in fig. 8, each element in the material can be found in the XPS spectrum, and the high-resolution spectra of Cu 2p and Cu LM2 can prove that Cu in the material is +1 valent.
As shown in FIG. 9, the UV-visible IR diffuse reflectance map demonstrates RO-4 and oxidized clusters { PMo } 8 V 6 O 42 Has a broad light absorption range of 300-1100nm. The light absorption range of the ligand and the complex CuL which is also composed of monovalent copper is narrow, which indicates that the light absorption unit is { PMo } 8 V 6 O 42 }. The band gap of RO-4 is calculated to be 1.75eV by utilizing a Kubelka-Munk formula, and the RO-4 is proved to have semiconductor-like characteristics. As shown in fig. 10, the position of the Lowest Unoccupied Molecular Orbital (LUMO) of RO-4 was calculated to be 1.15eV (vs. nhe, pH = 7) by ultraviolet photoelectron spectroscopy. As shown in FIG. 11, the band structure of RO-4 was determined by the band gap and the location of LUMO, and it was found that RO-4 could accomplish both water oxidation and CO oxidation simultaneously 2 Reducing to most of the reduction products (such as HCOOH, CO and the like). Meanwhile, as shown in FIG. 12, the position of the highest electron occupied orbital (HOMO) calculated by the Mott-Schottky diagram is-0.65V, which is consistent with the results in the band structure diagram. As shown in fig. 13, RO-4 was found to have a significant photocurrent response to light when switched periodically under illumination. The above characterization indicates that RO-4 is a potential photocatalyst.
5mg of RO-4 catalyst is put in a solid-gas photocatalytic reaction system for testing. The wavelength range of the light source is 300-1100nm. As shown in FIG. 14, only water vapor and CO are present 2 After four hours of reaction, RO-4 catalyzes CO 2 Reduction to CO (80.24. Mu. Mol/g) with a selectivity of more than 99.5% with simultaneous oxidation of water to O 2 . As shown in FIG. 15, RO-4 is only exchanging water and re-ventilating CO 2 In the case of (3), the reaction is cycled for four times, the performance is not obviously reduced, and the good cycling stability is proved. As shown in FIG. 16, the performance of the reaction can be continuously performed for 15 hours without significant deterioration, which is a great advantage in future industrial production.
Comparative example 1
The test procedure in this example was substantially the same as in example 1 above, except that the catalyst used in this example was { PMo } 8 V 6 O 42 }。
Comparative example 2
The test procedure in this example was essentially the same as in example 1 above, except that the catalyst used in this example was CuL.
When p-tr is used, as shown in FIG. 17 2 When the Ph ligand is a catalyst, no reduction product is found to be produced, demonstrating that p-tr 2 Ph is catalytically inactive, when CuL or { PMo is used 8 V 6 O 42 When the catalyst is used, 6.5 mu mol g of the catalyst is added -1 h -1 And 5.5. Mu. Mol g -1 h -1 When CuL and { PMo 8 V 6 O 42 After physical mixing according to the amount of the substances, the catalytic performance is 6 mu mol g -1 h -1 Much lower than when RO-4 is used as the catalyst (20.06. Mu. Mol g) -1 h -1 ) And the situation shows that electrons are rapidly transmitted after the oxidation site and the reduction site are coordinated, so that the catalytic reaction is more facilitated.
Claims (10)
1. A crystalline reduction-oxidation cluster-based complex characterized by the structural formula: cu 8 Cl[PMo 8 V 6 O 42 ](p-tr 2 Ph) 4 ·8H 2 O, the reduction element and the oxidation element of which are effectively combined and mutually coupled; the p-tr 2 Structural formula of PhThe following were used:
2. a method for preparing a crystalline reduction-oxidation cluster-based complex according to claim 1, wherein the hydrothermal synthesis is performed by a one-pot method, comprising the steps of: sequentially adding organic ligand 4,4' - (1, 4-phenyl) bis (4H-1, 2, 4-triazole), metal salt and phosphorus source H into a polytetrafluoroethylene high-pressure reaction kettle 3 PO 3 The tetrabutyl ammonium hydroxide aqueous solution and deionized water are mixed uniformly and heated, then cooled to room temperature, washed and dried, and the black spindle crystal is obtained.
3. The method of claim 2, wherein the metal salt comprises a vanadium salt, a molybdenum salt, and a copper salt, the vanadium salt being NH 4 VO 3 、NaVO 3 Or V 2 O 5 The molybdenum salt is Na 2 MoO 4 ·2H 2 O、(NH 4 ) 2 MoO 4 Or H 3 PMo 12 O 40 ·H 2 O, copper salt is CuCl 2 ·2H 2 O。
4. The method for preparing a crystalline reduction-oxidation cluster-based complex according to claim 3, wherein the mass ratio of the vanadium salt, the copper salt and the molybdenum salt in the metal salt is 1; the mass ratio of the metal salt to the organic ligand is 1.
5. The method of claim 2, wherein the volume of the reaction solution in the autoclave is 1/3-2/3.
6. The method of claim 2, wherein the heating is performed at 170-180 ℃ for 2.5-3 days.
7. Use of the crystalline reduction-oxidation cluster-based complex of claim 1 in the field of photocatalysis.
8. The use of a crystalline reduction-oxidation cluster-based complex in the field of photocatalysis according to claim 7, wherein the complex is used as a catalyst and is subjected to photocatalytic tests under carbon dioxide, argon or a mixture of carbon dioxide and argon.
9. Use of a reducing-oxidizing cluster-based complex according to claim 7, wherein the wavelength of the light source in the photocatalytic test is in the range of 300-1100nm.
10. Use of a reduction-oxidation cluster-based complex according to claim 7, wherein the carbon dioxide is catalytically reduced to carbon monoxide with a selectivity of 99.5% by a photocatalytic test.
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