CN116273180A - Catalyst of organic zinc complex and molybdenum sulfide heterostructure, preparation method and application - Google Patents
Catalyst of organic zinc complex and molybdenum sulfide heterostructure, preparation method and application Download PDFInfo
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- CN116273180A CN116273180A CN202211102902.7A CN202211102902A CN116273180A CN 116273180 A CN116273180 A CN 116273180A CN 202211102902 A CN202211102902 A CN 202211102902A CN 116273180 A CN116273180 A CN 116273180A
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- catalyst
- molybdenum sulfide
- heterostructure
- organic zinc
- zinc complex
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011701 zinc Substances 0.000 title claims abstract description 54
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 238000013032 photocatalytic reaction Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001741 organic sulfur group Chemical group 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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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
- B01J31/16—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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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Abstract
The invention discloses a catalyst of an organic zinc complex and molybdenum sulfide heterostructure, a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, preparing flaky molybdenum sulfide; step 2, preparing a layered organic zinc complex; step 3, dispersing molybdenum sulfide and organic zinc complex in solvent respectively, and dripping the solution containing the organic zinc complex into sulfur-containing solutionAnd (3) reacting in the molybdenum-dissolving solution, and centrifuging, washing, drying and roasting to obtain the catalyst. The invention adopts a simple mixed load method to compound two-dimensional semiconductors to form a heterostructure, thereby effectively solving the problem of CO 2 And H 2 O activation problem, and the adsorption energy of the reaction intermediate on the surface of the catalyst is regulated by regulating and controlling the proportion of two-dimensional semiconductors, so that the selectivity of the methanol of almost 90 percent is obtained, and the catalyst is photocatalytic CO 2 High value conversion provides a viable research strategy.
Description
Technical Field
The invention relates to the technical field of catalyst materials, in particular to a catalyst of an organic zinc complex and molybdenum sulfide heterostructure, a preparation method and application thereof.
Background
With the development of global industrialization, various organic chemicals are urgently needed in the society. In recent years, the environmental problems such as the increasing exhaustion of fossil resources and the greenhouse effect caused by the excessive use of fuel and the excessive discharge of carbon dioxide are promoted by CO 2 Has important significance for reducing emission of main greenhouse gases. Carbon capture and storage are important means to reduce carbon dioxide emissions, but they cannot fundamentally improve the problem of excessive carbon dioxide emissions in the short term. Solar energy is used as a renewable clean energy source, and the renewable clean energy source is used for catalyzing the reaction of carbon dioxide and water to prepare methanol, so that not only can environmental pressure be relieved, but also chemicals with high added value can be produced, and the renewable clean energy source can be used as a long-term development strategy of carbon emission reduction.
But to achieve photocatalytic CO 2 And H 2 The efficient preparation of methanol by the O reaction is not easy. Due to CO 2 And H 2 O is a relatively stable reaction molecule, and the photocatalytic activation of CO 2 And H 2 O relies on efficient separation of electron-hole and rapid charge transfer, while high selectivity for methanol production requires avoidance of CH 4 And the production of CO and other by-products. The two-dimensional semiconductor material is rich in defects, so that more sites can be provided for adsorbing and activating reactants, the electron transfer efficiency can be promoted, the reaction kinetics can be accelerated, the two-dimensional semiconductor material is widely used for photocatalytic reaction, the problem that electrons and holes are easy to quickly compound limits the improvement of the photoactive efficiency of a single two-dimensional material, and in recent years, a learner discovers that the inscribed electric field of the whole catalyst can be enhanced by compounding two semiconductor materials to form a heterojunction or a heterostructure, thereby avoiding the quick combination of electrons and holes and improving the photocatalytic activity.
But currently commonly used TiO 2 Most photocatalysts such as ZnO have a large band gap and absorb only light in the near UV region. Thus, only a small fraction of sunlight is utilized, with many low bandgap photocatalysts such as CdS and Fe 2 O 3 Exhibiting lower stability. To address these shortcomings, new catalysts must be investigated to meet the needs of future solar driven environmental and energy technologies.
CN111889112a discloses a MoS 2 Preparation method of Graphene two-dimensional material heterojunction visible light catalyst, preparing single-layer uniform Graphene on the surface of copper foil through a CVD method, transferring single-layer Graphene to the surface of a silicon dioxide substrate through wet transfer, and growing MoS on the surface of Graphene through a two-step CVD growth method 2 Preparing MoS 2 Graphene two-dimensional material heterojunction visible light catalyst, wherein Graphene has excellent conductivity and can accelerate MoS 2 The surface electrons are transmitted, and the heterojunction can improve the separation efficiency of electron holes at the interface, so that the photoelectrocatalysis efficiency of the composite material is improved. But MoS in this patent 2 The CVD method used for synthesizing/Graphene is complex, the related synthetic materials are more, the molybdenum foil is electroplated to increase the synthetic energy consumption, and the Graphene and MoS are grown 2 The required temperature of the material is extremely high and reaches 1200 ℃ and 800 ℃, which is contrary to the green synthesis concept of the material.
CN109759121a discloses a preparation method of a two-dimensional Z-type heterojunction visible light catalyst. The method comprises the following steps: preparation of block g-C by thermal polymerization 3 N 4 Dispersing the material in concentrated hydrochloric acid, heating at constant temperature, stirring and drying to obtain white powder A; adding the obtained white powder A into a dispersing agent solution, and peeling and drying through ultrasonic liquid phase to obtain white powder B; dispersing the obtained white powder B in deionized water, dropwise adding a mixed solution of bismuth nitrate pentahydrate and potassium bromide, heating and stirring, centrifuging the obtained precipitate after the reaction is finished, and drying to obtain the two-dimensional Z-type heterojunction visible light catalyst. However, the blocks g-C obtained in this patent 3 N 4 The material is thicker, which is detrimental to light absorption and transmission, and which remains after the addition of a certain amount of capture agent in catalytic applicationsThe desired activity is not achieved.
Disclosure of Invention
The present invention is directed to photocatalytic CO 2 And H 2 The catalyst can realize photocatalytic high-selectivity reduction of carbon dioxide, and obtain methanol chemicals with high value.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a catalyst of an organozinc complex and molybdenum sulfide heterostructure, comprising the steps of:
and 3, dispersing the flaky molybdenum sulfide and the lamellar organic zinc complex in a solvent respectively, dripping a solution containing the organic zinc complex into the solution containing the molybdenum sulfide for reaction, and centrifuging, washing, drying and roasting to obtain the catalyst.
The invention loads the organic zinc complex on the flaky molybdenum sulfide through simple stirring, roasting and other processes to form a novel heterostructure, and the obtained catalyst greatly improves CO 2 Adsorption activation of H in a photocatalytic reaction 2 Efficient reduction of CO by O 2 Is a catalyst activity of (a). The catalyst has light absorption characteristic, can generate sufficient electron-hole pairs under the illumination condition, improves the separation and transmission efficiency of photo-generated carriers, and effectively inhibits the rapid recombination of the electron-hole pairs, thereby participating in H efficiently 2 Oxidation process of O and CO 2 In the reduction process, the yield of the target product methanol can be effectively improved.
The molybdate comprises one or more of sodium molybdate, nickel molybdate and ammonium molybdate;
the organic sulfur-containing compound comprises one or more than two of mercaptan, thiophenol, thiourea and disulfide;
the zinc salt comprises one or more than two of zinc nitrate, zinc carbonate and zinc chloride;
the bipyridyl includes 2, 2-bipyridine and/or 4, 4-bipyridine.
The above organic sulfur-containing compound, zinc salt and bipyridine react to easily form an organozinc complex.
In the step 1, the molar ratio of the organic sulfur compound to the molybdate is 0.5 to 60:0.5-30; preferably in a molar ratio of 0.5 to 30:0.5-15.
In the step 1, stirring and mixing are carried out for 2-48 hours at room temperature; room temperature is 5-40 ℃; for example, stirring at 10-35℃for 4-24 hours, 6-12 hours, 6-10 hours, 8 hours, etc.; the crystallization temperature is 100-300 ℃ and the time is 8-30 hours; for example, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, essence for 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours and 28 hours, preferably, the crystallization temperature is 160-200 ℃ and the crystallization time is 8-12 hours.
In the step 2, the molar ratio of the zinc salt to the dipyridine to the oxalic acid is 0.5-80:0.5-80:0.5-80; preferably in a molar ratio of 0.5 to 20:0.5-20:0.5 to 20, more preferably 0.5 to 8:0.5-8:0.5-5
In the step 2, the dispersing temperature is 10-50 ℃ and the dispersing time is 2-48h, such as 4h, 8h, 10h, 12h, 16h, 18h, 24h and 36h; preferably, the dispersion temperature is 20-40 ℃ and the dispersion time is 2-6h;
preferably, zinc salt, bipyridine and oxalic acid can be singly dispersed in a solvent in advance, and then the three solutions are mixed for dispersion to prepare the layered organic zinc complex, so that the dispersion in advance is beneficial to the uniform dispersion of all substances and the reaction efficiency is improved.
In the step 3, the mass ratio of the organic zinc complex to the molybdenum sulfide is 1-300:20-200 parts; the preferable mass ratio is 1-200:50-200, more preferably 1-160:100-200. The mass ratio of the two components has important influence on the formation of a heterostructure, the content of the organic zinc complex is too low, so that the heterostructure of the organic zinc complex and molybdenum sulfide is not facilitated, a dispersed two-phase structure is easy to form, and finally, the transfer of a photon-generated carrier in the photocatalyst is not facilitated, and the reaction activity is reduced; however, excessive organic zinc complex can cover the molybdenum sulfide carrier and the heterostructure formed by the molybdenum sulfide carrier and the molybdenum sulfide carrier, the reactive sites are obviously reduced, and the photoactivity of the catalyst is weakened. The final catalyst performance is excellent at this ratio.
In the step 3, the reaction temperature is 10-50 ℃ and the reaction time is 2-56h;
in the step 3, the roasting temperature is 30-450 ℃ and the roasting time is 2-20h; preferably, the firing temperature is 30 to 400 ℃, further preferably 100 to 300 ℃, still further preferably 200 to 300 ℃; when the roasting temperature is lower, the formation of a heterostructure is not facilitated, and the catalytic activity is weakened; when the roasting temperature is too high, the catalyst is agglomerated, the stacking of the multi-layer catalyst is unfavorable for electron transfer, and finally the reactivity is reduced.
The solvent comprises water and alcohols, wherein the alcohols comprise methanol, ethanol, glycol, n-butanol, benzyl alcohol and the like;
washing the products in the steps 1-3 by adopting a specific solvent, and drying at 60-80 ℃ for 1-6 hours or 1-8 hours.
The invention also provides a catalyst of the organic zinc complex and molybdenum sulfide heterostructure prepared by the preparation method.
The catalyst consists of a layered organic zinc complex and flaky molybdenum sulfide, wherein the thickness of the flaky molybdenum sulfide is 1-50nm, the single layer thickness of the layered organic zinc complex is 1-10nm, and the total thickness of the catalyst is 2-100nm.
The mass content of zinc element in the catalyst is not higher than 50wt%. The zinc element content has a larger influence on the catalytic performance of the product, and when the zinc element content is lower, the formation of a heterostructure is not facilitated; when the content of zinc element is high, the organic zinc complex layer can cover the carrier molybdenum sulfide and the heterostructure formed by the carrier molybdenum sulfide and the carrier molybdenum sulfide, and finally the reactivity is reduced. Preferably, the zinc element content is 0.1-10wt%; it is more preferable that the content of zinc element is 0.5 to 10wt%, and it is still more preferable that the content of zinc element is 0.5 to 5wt%. In this range, as the Zn element loading increases, its CO 2 And H is 2 O has gradually improved photocatalytic activity, methanol yield and methanol at 5wt%The selectivity reaches a maximum.
The invention also provides the application of the catalyst in preparing methanol by photocatalytic carbon dioxide reduction, which is characterized in that the photocatalytic reaction is carried out under the conditions of 25-200 ℃ and 1-10MPa, the light source is a xenon lamp with the light source of 100-600W, and the methanol yield is 130 mu mol gcat -1 ·h -1 The selectivity of methanol is more than 75 percent; preferably, the methanol yield is 148. Mu. Mol. Gcat -1 ·h -1 The selectivity of methanol is above 78;
further preferably, the methanol yield is 200. Mu. Mol. Gcat -1 ·h -1 The selectivity of the methanol is more than 80 percent;
further, the methanol yield was 400. Mu. Mol. Gcat -1 ·h -1 The selectivity of the methanol is more than 90 percent; the catalyst obtained by the invention can promote H under the conditions of low temperature and low pressure under the illumination 2 Reduction of CO by O 2 High-value chemicals such as methanol and the like are obtained, and the selectivity and the yield of the methanol are greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a simple mixed load method to compound two-dimensional semiconductors to form a heterostructure, thereby effectively solving the problem of CO 2 And H 2 O activation problem, and the adsorption energy of the reaction intermediate on the surface of the catalyst is regulated by regulating and controlling the proportion of two-dimensional semiconductors, so that the selectivity of the methanol of almost 90 percent is obtained, and the catalyst is photocatalytic CO 2 High value conversion provides a viable research strategy.
(2) The catalyst prepared by the invention has light absorption property, so that sufficient electron-hole pairs can be generated under the illumination condition, the separation and transmission efficiency of photo-generated carriers is improved, and the rapid recombination of electron-hole is effectively inhibited, thereby participating in H with high efficiency 2 Oxidation process of O and CO 2 A reduction process capable of promoting H at low temperature and low pressure 2 Reduction of CO by O 2 The selectivity and the yield of the methanol are greatly improved, and the yield of the methanol is 130 mu mol gcat -1 ·h -1 The selectivity of methanol is above 75%.
(3) Compared with the conventional catalyst, the preparation process of the catalyst with the organic zinc complex and molybdenum sulfide heterostructure is simple, the operation is easy, the raw materials are simple and easy to obtain, the catalyst has industrial application potential, and the catalyst is suitable for popularization and application.
Drawings
FIG. 1 is a schematic illustration of the preparation of heterostructure catalysts and MoS from example 1 2 Is an X-ray diffraction pattern of (c).
Fig. 2 is a TEM image (a), an EDX image (b) and an EDX image (c) of each element in the catalyst for preparing the heterostructure catalyst of example 1.
FIG. 3 is a schematic illustration of the preparation of heterostructure catalysts for catalyzing CO in examples 1-5 of application 2 And H 2 Comparison of methanol performance prepared by O.
FIG. 4 is a schematic illustration of the preparation of heterostructure catalysts and other catalysts for the catalytic CO in example 1 2 And H 2 Comparison of methanol performance prepared by O.
FIG. 5 is a schematic illustration of the preparation of heterostructure catalysts for catalyzing CO in examples 6-9 of application 2 And H 2 Comparison of methanol performance prepared by O.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials adopted in the following specific embodiments are purchased from the Ala-dine or the Chinese medicinal reagent and are directly used without treatment.
Example 1
step 3, respectively preparing two solutions, D:200mg of molybdenum sulfide is dispersed in 30ml of deionized water by ultrasonic wave; e:77mg of organic zinc complex is dispersed in 30ml of deionized water by ultrasonic, after the two solutions are dispersed uniformly, then E solution is dropwise added into D solution, the solution is reacted for 18 hours at 30 ℃, the obtained product is placed in a muffle furnace after washing, centrifuging and drying, the roasting temperature is increased from 50 ℃ to 300 ℃, and the roasting is kept at 300 ℃ for 15 hours, so that the catalyst of the heterostructure of the organic zinc complex and molybdenum sulfide is obtained, and the catalyst is marked as 5Zn@MoS 2 ；
The zinc content in the heterostructure catalyst prepared by the calculation of the input ratio of the raw materials is 5wt%. FIG. 1 shows a catalyst of heterogeneous structure of prepared organozinc complex 5Zn@MoS 2 And the X-ray diffraction pattern of the molybdenum sulfide prepared in the step 1. As can be seen from FIG. 1, the crystal structure of molybdenum sulfide is not changed after the organic zinc complex is loaded on the molybdenum sulfide, but 5Zn@MoS is compared with the unloaded molybdenum sulfide 2 Characteristic diffraction peaks of the organozinc complex appear in the XRD pattern of (c).
FIG. 2 (a) is a TEM image of a 5wt% organozinc complex prepared with a molybdenum sulfide heterostructure catalyst. As can be seen from fig. 2 (a), the organozinc complex exhibits a more pronounced lamellar structure, which is intimately associated with both surfaces of the sheet-like molybdenum sulfide, exhibiting heterostructure characteristics. This phenomenon was also demonstrated in the EDX map of 5wt% organozinc complex with molybdenum sulfide heterostructure catalyst (as shown in fig. 2 (b) (c)).
The thickness of flaky molybdenum sulfide in the catalyst obtained by microscopic morphology measurement is 2nm, the single-layer thickness of the layered organic zinc complex is 2nm, and the total thickness of the material is 3-4nm.
Examples 2 to 5
According to the preparation process of example 1, the input ratio of the organozinc complex and molybdenum sulfide in the step 3 is changed to be 1.54: 200. 7.7: 200. 15.4: 200. 154:200, and preparing heterostructure catalysts with zinc loading of 0.1wt%, 0.5wt%, 1wt% and 10wt% respectively.
Examples 6 to 9
According to the preparation process of example 1, the roasting temperature in the step 3 is changed to be 30 ℃, 100 ℃, 350 ℃ and 400 ℃ respectively, and 5Zn@MoS at different roasting temperatures is prepared 2 。
Comparative example 1
According to the preparation process of example 1, zn-MoS was obtained without a calcination step 2 。
Comparative example 2
Three solutions were prepared, a:714mg of zinc nitrate are dispersed in 30ml of deionized water by ultrasonic wave; b:348mg of 2,2' -bipyridine are ultrasonically dispersed in 15ml of methanol; c:120mg of oxalic acid is dispersed in 20ml of deionized water by ultrasonic, after the three solutions are uniformly dispersed, the solution B and the solution C are respectively added into the solution A dropwise (the molar ratio of zinc nitrate, 2' -bipyridine and oxalic acid is 2.4:2.2:1.0), after stirring for 3 hours at 30 ℃, the white powdery catalyst is obtained after centrifugation, washing and drying, and the white powdery catalyst is placed at 400 ℃ for roasting for 15 hours, so as to obtain zinc oxide.
Two solutions were prepared separately, D:200mg of molybdenum sulfide is dispersed in 30ml of deionized water by ultrasonic wave; e:77mg of zinc oxide is dispersed in 30ml of deionized water by ultrasonic, after the two solutions are dispersed uniformly, the E solution is dropwise added into the D solution, the reaction is carried out for 18 hours at 30 ℃, the obtained product is placed in a muffle furnace after washing, centrifuging and drying, the roasting temperature is increased from 50 ℃ to 300 ℃, the roasting is carried out for 15 hours at 300 ℃, and the zinc oxide and molybdenum sulfide heterostructure catalyst is obtained and is marked as ZnO@MoS 2 . Evaluation of the Performance of the catalysts of application examples 1-9 and comparative examples 1-2
The catalysts prepared in examples 1-9 and the catalysts of comparative examples 1-2 were subjected to photocatalytic performance evaluation, and the photocatalytic reaction was performed in a specially-made quartz-type high-pressure reaction apparatus, and the light energy emitted from a xenon lamp passed through a quartz glass reactor to reach the surface of the catalyst, so as to achieve the photocatalytic reaction.
Reaction conditions: 90mg of catalyst was dispersed in the above-mentioned quartz reactor before the photocatalytic reaction, and 20mL of deionized water was injected, followed by introduction of CO at 6MPa 2 Exhausting the air from the reactor, followed by CO 2 Pressurizing to 6Mpa. Illuminating with 500W xenon lamp at 25deg.C, and using cutoff filter<420 nm) to filter out ultraviolet light in the illumination. After controlling the reaction time, the relevant products were quantified by gas chromatography and nuclear magnetic resonance analysis.
Table 1 methanol yield and selectivity of the catalysts of examples and comparative examples
Tables 1 and 3 are graphs of methanol yields of the different loadings of organozinc complexes prepared in examples 1-5 with molybdenum sulfide heterostructure catalysts, from which it can be seen that zinc loading has an effect on the photocatalytic performance of the catalysts. As can be seen from FIG. 3, the reaction performance of preparing methanol by reducing carbon dioxide is remarkably improved after the organic zinc complex is loaded on molybdenum sulfide, and the methanol yield can reach 688.86 mu mol gcat especially when the loading is 5wt% -1 ·h -1 This shows that the catalyst has good photocatalytic reaction activity and can effectively promote the generation of methanol products.
Tables 1 and 4 show the two precursors prepared, zinc oxide and molybdenum sulphide heterostructure catalysts and 5wt% Zn@MoS 2 The reactivity of (3) is compared with the graph. As can be seen from FIG. 4, 5wt% Zn@MoS 2 Shows a better methanol yield, which is significantly higher than MoS 2 (60μmol·gcat -1 ·h -1 ) Organozinc complexes (110. Mu. Mol. Gcat) -1 ·h -1 )、ZnO@MoS 2 (102μmol·gcat -1 ·h -1 ). By contrast, the catalyst has good light compared with a part of heterostructure catalyst and a common two-dimensional photocatalystCatalytic activity and effectively promoting methanol generation.
Table 1 and FIG. 5 show the 5wt% Zn@MoS synthesized at different calcination temperatures prepared 2 The reactivity of (3) is compared with the graph. As can be seen from fig. 5, the calcination temperature was 300 c, which showed a good methanol yield, significantly higher than the other calcination temperatures. This shows that at 300℃firing temperature, the Zn precursor and MoS 2 The method can form a relatively stable heterostructure, effectively promote the transfer of electrons between two-dimensional materials, avoid the recombination of holes and electrons, and further improve the production of methanol.
Catalyst 5Zn@MoS prepared in example 1 2 Compared with the performance of the catalyst for photocatalytic carbon dioxide reduction reported in some documents in the prior art, the results are shown in table 2, and compared with the catalyst in some documents under the photocatalytic condition, the organic zinc complex and the molybdenum sulfide heterostructure catalyst have stronger photocatalytic selective reduction capability of carbon dioxide, and can produce chemicals such as methanol, oxygen and the like with high added value, so that the catalyst has high-efficiency photocatalytic effect, the problem of high-speed recombination of electron hole pairs is relieved to a certain extent, and the reaction activity of photocatalytic carbon dioxide reduction can be effectively improved.
Table 2 comparison of the photocatalytic carbon dioxide reduction performance of the catalyst of example 1 with the literature catalyst
Claims (10)
1. A method for preparing a catalyst of an organozinc complex and molybdenum sulfide heterostructure, which is characterized by comprising the following steps:
step 1, stirring and mixing molybdate and an organic sulfur-containing compound in a solvent, crystallizing and washing to obtain flaky molybdenum sulfide;
step 2, mixing zinc salt, bipyridine and oxalic acid in a solvent, dispersing and washing to obtain a layered organic zinc complex;
and 3, dispersing the flaky molybdenum sulfide and the lamellar organic zinc complex in a solvent respectively, dripping a solution containing the organic zinc complex into the solution containing the molybdenum sulfide for reaction, and centrifuging, washing, drying and roasting to obtain the catalyst.
2. The method for preparing a catalyst of an organozinc complex and molybdenum sulfide heterostructure according to claim 1, wherein the molybdate comprises one or a combination of two or more of sodium molybdate, nickel molybdate, and ammonium molybdate;
and/or the organic sulfur-containing compound comprises one or more than two of mercaptan, thiophenol, thiourea and disulfide.
3. The method for preparing the catalyst of the heterostructure of the organic zinc complex and the molybdenum sulfide according to claim 1, wherein the zinc salt comprises one or a combination of more than two of zinc nitrate, zinc carbonate and zinc chloride; and/or the bipyridine comprises 2, 2-bipyridine and/or 4, 4-bipyridine.
4. The method for preparing a catalyst of an organozinc complex and molybdenum sulfide heterostructure according to claim 1, wherein in step 1, the molar ratio of the organosulfur compound to molybdate is 0.5 to 60:0.5-30; stirring and mixing for 2-48h at room temperature; the crystallization temperature is 100-300 ℃ and the time is 8-30h.
5. The method for preparing the catalyst of the heterostructure of the organic zinc complex and the molybdenum sulfide according to claim 1, wherein in the step 2, the molar ratio of zinc salt, bipyridine and oxalic acid is 0.5-80:0.5-80:0.5-80; the dispersing temperature is 10-50 ℃ and the dispersing time is 2-48h.
6. The method for preparing the catalyst of the heterostructure of the organic zinc complex and the molybdenum sulfide according to claim 1, wherein in the step 3, the mass ratio of the organic zinc complex to the molybdenum sulfide is 1-300:20-200 parts; the reaction temperature is 10-50 ℃ and the reaction time is 2-56h; roasting temperature is 30-450 ℃ and roasting time is 2-20h.
7. The method for preparing a catalyst of an organozinc complex heterostructure with molybdenum sulfide according to claim 1, characterized in that the solvent comprises water and/or alcohols.
8. The catalyst of the heterostructure of the organic zinc complex and the molybdenum sulfide, which is prepared by the preparation method according to any one of claims 1 to 7, wherein the catalyst consists of lamellar organic zinc complex and lamellar molybdenum sulfide, the lamellar molybdenum sulfide has a thickness of 1 to 50nm, the monolayer thickness of the lamellar organic zinc complex is 1 to 10nm, and the total thickness of the catalyst is 2 to 100nm; the mass ratio of zinc element in the catalyst is not higher than 50wt%.
9. Use of the catalyst according to claim 8 for the preparation of methanol by photocatalytic carbon dioxide reduction.
10. The use of the catalyst according to claim 9 for preparing methanol by photocatalytic reduction of carbon dioxide, wherein the photocatalytic reaction is performed at 25-200 ℃ under 1-10MPa with a xenon lamp as light source of 100-600W and a methanol yield of 130 μmol gcat -1 ·h -1 The selectivity of methanol is above 75%.
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