CN109331883A - A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application - Google Patents
A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application Download PDFInfo
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- CN109331883A CN109331883A CN201811414538.1A CN201811414538A CN109331883A CN 109331883 A CN109331883 A CN 109331883A CN 201811414538 A CN201811414538 A CN 201811414538A CN 109331883 A CN109331883 A CN 109331883A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 230000001699 photocatalysis Effects 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 51
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 35
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
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- 239000007788 liquid Substances 0.000 claims description 11
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- NYGZKMXIYAFNRM-UHFFFAOYSA-N methanol;zinc Chemical compound [Zn].OC NYGZKMXIYAFNRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 239000003446 ligand Substances 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 8
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- 238000010531 catalytic reduction reaction Methods 0.000 description 19
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- 239000004065 semiconductor Substances 0.000 description 15
- 238000011056 performance test Methods 0.000 description 10
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- 239000011701 zinc Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- -1 PdS Chemical compound 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000012797 qualification Methods 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910005833 GeO4 Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- B01J35/60—
-
- B01J35/61—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention discloses a kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application, composite photocatalyst material is modified by metal organic frame and is constituted in CdS nanoparticle surface.Composite catalyzing material the preparation method comprises the following steps: first passing through solvent structure CdS nanoparticle, again by heterogeneous sedimentation in situ in the nanoparticle surface modified metal organic frame of CdS, up to CdS/ metal organic frame composite photocatalyst material, the relatively existing CdS of the CdS/ metal organic frame composite photocatalyst material, optical stability, the transformation efficiency of photocatalytic reduction of carbon oxide and cyclical stability and catalytic selectivity are improved significantly.
Description
Technical field
The present invention relates to a kind of catalysis materials, in particular to a kind of to be modified by metal organic frame in CdS nanoparticle
The CdS/ metal organic frame composite photocatalyst material that surface is constituted, and be related to solvent-thermal method and combine heterogeneous sedimentation in situ
The method for preparing CdS/ metal organic frame composite photocatalyst material further relates to CdS/ metal organic frame composite photocatalyst material
Application on catalysis reduction carbon dioxide, belongs to catalysis material preparation technical field.
Background technique
Light-catalyzed reaction is to be found by Japanese Scientists Fujishima and Honda in 1972 earliest, they are using closely
Ultraviolet light TiO2Water decomposition is successfully oxygen and hydrogen by electrode.It is more and more with gradually going deep into for photocatalysis research
Semiconductor material be developed for use in photocatalysis experiment, such as BiVO4、Bi2WO6、InTaO4、NaNbO3、Zn2GeO4、C3N4、
Cu2O、In2O3With perovskite etc..Different semiconductor materials because its band structure and self-characteristic, photocatalysis effect are had nothing in common with each other,
Same semiconductor material, by the regulation to its size, pattern and structure, or in the compound other materials of its surface modification,
Its photocatalysis effect can be improved.
Size by reducing nano material can increase the specific surface area of catalyst, facilitate to reactant adsorption capacity
The increase of enhancing and reactivity site, there is also quantum effect, material surface when nano material size is small to a certain extent
The regulation in vacancy can change the electricity and chemical property of semiconductor surface, is conducive to the absorption and activation of reactant, passes through tune
Control its adjustable electronic band structure of crystal face, surface energy, surface-active site etc. of semiconductor exposure.In addition, can also pass through
In the compound other materials of semiconductor material surface modification, its photocatalysis performance is improved.It is helped in semiconductor material surface load
Catalyst can form Schottky barrier with semiconductor, promote the separation and circuitous shifting of photo-generated carrier, reduce electron hole pair
Recombination probability.Common co-catalyst has noble metal nano particles (Pt, Au, Ag etc.) and metal oxide (Cu2O and RuO2) etc.,
Better electric conductivity and lower overpotential can be obtained by load cocatalyst, co-catalyst can also influence product selection
Property, the type by changing co-catalyst can change product species.And the modification of certain semiconductor material surface it is compound it is upper its
His semiconductor material can expand light abstraction width, improve sun light utilization efficiency, at the same promote the separation of photo-generate electron-hole with
Circuitous shifting reduces the compound of electron hole pair, to improve photocatalysis effect.
Energy crisis is the problem faced at present, now our main or fossil energies for utilizing, as petroleum,
Coal, natural gas etc..Fossil energy is non-renewable resources after differentiation in millions of years, with the quick hair of modern industry
Exhibition, fossil energy are constantly consumed, and reserves are fewer and fewer.Investigation at the beginning of 21 century shows in current reserves and opens
Adopt under speed, natural gas can mining time be 60 years or so, coal is 230 years or so, and petroleum is 40 years or so.It is another
Aspect, the burning of a large amount of fossil energies cause carbon dioxide (CO2) isothermal chamber gas excessive emissions, caused a series of
Global environmental problem threatens the survival and development of the mankind.It therefore, if can be by the CO of excess emissions2It is converted into an oxygen
The chemical products of changing the high added values such as carbon, methane, methanol, formic acid and carbonic ester, can not only reduce the mankind to fossil energy according to
Rely, also can effectively reduce CO in atmosphere2Discharge.CO2Trapping and conversion (Carbon Capture and Conversion,
It CCC) is considered as reducing CO at this stage2Discharge improves one of the effective ways of the C1 utilization of resources.
CO2Macroscopic property it is highly stable, to realize CO2Effective conversion, it is necessary to input higher energy such as heat
Energy, electric energy and solar energy etc..Current artificial CO2Transformation technology mainly have bioconversion, thermochemical study, electrochemical conversion and
Photocatalytic conversion.These artificial CO2In method for transformation, thermochemical study and electrochemical conversion need to use thermal energy and electric energy, greatly
Part is also derived from fossil energy, and has biggish energy loss in conversion process.Photocatalytic conversion mainly utilizes solar energy,
It is direct energy input, and widely distributed.In addition, photo catalytic reduction CO2Reaction condition require also not high, normal temperature and pressure
Under can carry out, be very promising CO2Method for transformation.1978, Israel scientist Halmann used P-type semiconductor
GaP is as optoelectronic pole, by CO under illumination condition2It is reduced to CH3OH.And then in 1979, Tokyo Univ Japan Inoue etc.
Utilize WO3、TiO2, a series of semiconductor material such as CdS, GaP and SiC are to CO2It carries out photo catalytic reduction and obtains CO, CH4、CH3OH
With the multi-products such as HCOOH, and conductor photocatalysis reduction CO is analyzed2Reaction mechanism.
Sulfide semiconductor is common semiconductor light-catalyst.In general, the valence band of sulfide semiconductor is by S3PRail
Road is constituted, and corresponding oxide is compared, and valence band location is deviated to negative direction, and its conduction band also tends to bear partially, from
And make light induced electron that there is stronger reducing power, be conducive to improve photo catalytic reduction CO2Efficiency.Much sulfide (such as PdS,
Bi2S3) forbidden bandwidth it is smaller, absorb band edge can extend to infrared region, be relatively common photosensitizer.Partial vulcanization object
Such as CdS, oneself is applied to photo catalytic reduction CO2, forbidden bandwidth is about 2.4eV, absorbs band edge in 520nm, is had visible well
Photoresponse, can be efficiently under visible light illumination by CO2It is reduced to CO and other hydrocarbons.But CdS is in illumination
Under it is unstable, be easy to happen autoxidation, generate sulphur simple substance, that is, so-called photoetch phenomenon.In addition, simple CdS ratio
Surface area is smaller, to CO2Adsorption capacity it is weaker, in catalytic reaction process due to gas-particle two-phase interface dynamical resistance compared with
Greatly, cause transformation efficiency lower, while CdS is catalyzed CO2The selectivity for being reduced to CO is poor.
Summary of the invention
For defect existing for CdS catalysis material in the prior art, the first purpose of this invention is to be to provide one
Kind CdS/ metal organic frame composite photocatalyst material；The composite photocatalyst material is repaired by carrying out surface in CdS catalysis material
Metal organic frame is adornd, its optical stability and photocatalytic reduction of carbon oxide transformation efficiency can be effectively improved, can also be improved
Catalytic selectivity.
Second object of the present invention is to be to provide described in easy to operate, at low cost, mild condition the preparation of one kind
The method of CdS/ metal organic frame composite photocatalyst material.
Third object of the present invention is to be to provide a kind of CdS/ metal organic frame composite photocatalyst material be catalyzed
CO2Application in reduction, it is good to show stability, high catalytic efficiency, the good advantage of selectivity.
In order to achieve the above technical purposes, the present invention provides a kind of CdS/ metal organic frame composite photocatalyst material,
It is modified by metal organic frame and is constituted in CdS nanoparticle surface.
The relatively existing CdS catalysis material of CdS/ metal organic frame composite photocatalyst material of the invention, passes through gold
Belong to organic frame (MOF) to be surface modified CdS, generates apparent cooperative synergism effect, can effectively improve the light of CdS
The transformation efficiency and catalytic selectivity of electrical stability and its photocatalytic reduction of carbon oxide.CdS/ metal of the invention has machine frame
Frame composite photocatalyst material has typical core-shell structure, and kernel is CdS nanoparticle, itself has nanometer size effect,
Specific surface area is high, and active site is more, and metal organic frame growth in situ constitutes shell in CdS nanoparticle surface, gold
Belong to organic frame sheet as porous material, with high porosity and high-specific surface area, to CO2Adsorption capacity is obviously than CdS
By force, it is more advantageous to photo catalytic reduction CO2The progress of reaction.In addition, metal organic frame and CdS perfection are compound, metal has machine frame
Frame can be improved the photostability of CdS nanoparticle, extend the service life of photochemical catalyst, and cyclical stability increases.And in CdS
Nanoparticle surface modified metal organic frame, can be under the premise of not influencing the light absorption and band structure of CdS, and photoelectric current is more
Add stabilization.In addition, the CdS after CdS/ZIF-8 modification has preferably reduction selectivity relative to CdS, reduzate can be improved
The ratio of middle carbon monoxide.
Preferred scheme, the metal organic frame are ZIFs, such as ZIF-8, ZIF-67 etc..
The present invention also provides a kind of preparation method of CdS/ metal organic frame composite photocatalyst material, this method be with
Thiocarbamide and cadmium salt are raw material, by solvent structure CdS nanoparticle, then by heterogeneous sedimentation in situ at CdS nanometers
Particle surface modified metal organic frame is to get CdS/ metal organic frame composite photocatalyst material.
Preferred scheme will carry out solvent thermal reaction containing the organic solution of thiocarbamide, cadmium salt and dispersing agent to get CdS nanometers
Particle.
The molar ratio of more preferably scheme, thiocarbamide and cadmium salt is 0.2:1~5:1.
The molar ratio of more preferably scheme, thiocarbamide and dispersing agent is 0.5:1~3:1；The dispersing agent is PVP.
More preferably scheme, solvent is ethylene glycol in organic solution.
More preferably scheme, the temperature of the solvent thermal reaction are 100~180 DEG C, the time is 4~for 24 hours.
The present invention is conducive to obtain under the conditions of preferred solvent thermal reaction the CdS nanoparticle of suitable morphology and size.
Technical solution of the present invention is cooled to room temperature after the completion of solvent thermal reaction, by reaction solution, adds in reaction solution
Enter proper amount of methanol, to promote CdS nanoparticle to precipitate.Reaction solution is centrifuged again, precipitating is collected, washs and be freeze-dried, i.e.,
Obtain CdS nanoparticle.
Preferred scheme sequentially adds metal salt solution and the stirring of organic ligand solution in CdS nanoparticle dispersion liquid
Reaction, is centrifugated after the reaction was completed to get CdS/ metal organic frame composite photocatalyst material.Metal salt is first added in the present invention
Solution reaction, adding organic ligand solution reaction can guarantee metal organic frame in CdS nanoparticle surface even compact
Growth.The electronegative feature of CdS nanoparticle is mainly utilized, metal salt is first added, so that metal cation is first adsorbed on CdS and receives
Rice corpuscles surface, adds organic ligand compound, guarantees that uniformly and intimately growing metal in CdS nanoparticle surface has machine frame
Frame.
Centrifugal rotational speed of the invention is preferably 1000~3000rpm, wherein centrifugal rotational speed is too low, and CdS/ metal has machine frame
Frame compound cannot precipitate completely, and centrifugal rotational speed is excessively high, and CdS/ metal organic frame compound cannot be with gold free in solution
Belong to organic frame to efficiently separate.
The volume ratio of more preferably scheme, CdS nanoparticle dispersion liquid and metal salt solution and organic ligand solution is 5~
100:20~500:20~500.
More preferably scheme, the concentration of the CdS nanoparticle dispersion liquid are 1~20mg/mL.
More preferably scheme, the concentration of the metal salt solution are 5~100mM.
More preferably scheme, the concentration of the organic ligand solution are 5~400mM.
More preferably scheme, the CdS nanoparticle dispersion liquid is using methanol as solvent.
More preferably scheme, the metal salt solution are zinc salt methanol solution.
More preferably scheme, the organic ligand solution are 2-methylimidazole methanol solution.
More preferably scheme, it is 0.5~3h that the time being stirred to react after metal salt solution, which is added, and organic ligand solution is added
The time being stirred to react afterwards is 0.5~6h.
The method that the present invention prepares CdS/ metal organic frame composite photocatalyst material is non-using solvent-thermal method and original position
Phase sedimentation combines.Evengranular nanoscale CdS particle can be obtained by solvent-thermal method, nano-grade size can increase
CdS specific grain surface product, facilitates the enhancing to reactant adsorption capacity and the increase in reactivity site.In conjunction in situ non-
Homogeneous precipitation method can guarantee metal organic frame in CdS particle surface modified metal organic frame, heterogeneous sedimentation in situ
Uniformly and fully grown in CdS particle surface.
The present invention also provides a kind of applications of CdS/ metal organic frame composite photocatalyst material, are applied to photocatalysis also
Former carbon dioxide.
The method that CdS/ metal organic frame carries out photocatalytic reduction of carbon oxide in the present invention are as follows: first in acetonitrile and water
A certain amount of photochemical catalyst, 2,2'- bipyridyl, TEOA and CoCl is added in the in the mixed solvent of composition2, it is uniformly dispersed, then should
Mixed solution is transferred in the high airproof quartz reactor of quartz cover thoroughly, and carries out magnetic agitation, is held in the reaction system
It is continuous to be passed through CO2It is after a period of time that system is closed under an atmospheric pressure carbon dioxide, it is shone with xenon lamp from reactor head
It penetrates, controls light intensity and temperature of reaction system is constant, the gas-phase product in reaction process carries out qualitative and quantitative by gas-chromatography
Analysis.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1, CdS is unstable under light illumination, is easy to happen autoxidation, generates sulphur simple substance, that is, so-called photoetch shows
As.In addition, simple CdS specific surface area is smaller, to CO2Adsorption capacity it is weaker, due to gas-solid two in catalytic reaction process
The dynamical resistance of phase interface is larger, causes transformation efficiency lower.And the present invention passes through in CdS photocatalyst surface modified metal
After organic frame (MOF), the optical stability of CdS, the transformation efficiency of photocatalytic reduction of carbon oxide can be effectively improved and followed
Ring stability and catalytic selectivity.
2, CdS/ metal organic frame composite photocatalyst material of the invention is after CdS surface modification ZIF-8, to CdS's
Light absorption and band structure influence less, and photoelectric current is more stable, effectively improves its photostability.
3, CdS/ metal organic frame composite photocatalyst material of the invention has high hole due to the ZIF-8 crystal of load
Degree, low-density and high-specific surface area, CdS/ZIF-8 are more much higher than CdS to the adsorbance of nitrogen and carbon dioxide, are more advantageous to
Photo catalytic reduction CO2The progress of reaction.
4, CdS/ metal organic frame composite photocatalyst material of the invention is in photocatalytic reduction of carbon oxide performance,
CdS/ZIF-8 shows clear superiority with respect to CdS, and the generating rate of the two CO is respectively 32.13 μm of ol h-1With 26.33 μm of ol
h-1, performance boost about 22.03%.And CdS/ZIF-8 has better CO selectivity relative to CdS, shows in cyclic process
Higher stability.
5, CdS/ metal organic frame composite photocatalyst material preparation method of the invention is simple, mild condition, at low cost,
Be conducive to large-scale production.
Detailed description of the invention
[Fig. 1] is the XRD spectra of CdS/ZIF-8 made from embodiment 1, spreading out at 2 θ=7.4 °, 12.8 ° and 18.1 °
Peak is penetrated, ZIF-8 nanocrystal, the diffraction at 2 θ=24.9 °, 26.5 °, 28.2 °, 43.8 °, 47.8 ° and 51.9 ° are corresponded to
Peak corresponds to CdS nanoparticle, effectively illustrates that the success of CdS and ZIF-8 are compound.
The XPS characterization that [Fig. 2] is CdS/ZIF-8 made from embodiment 1.
[Fig. 3] is the micromorphology analysis figure of CdS made from CdS/ZIF-8 made from embodiment 1 and comparative example 1；Wherein,
Scheme the SEM that a is CdS to scheme；Scheme the SEM that b is CdS/ZIF-8 to scheme；It will be clear that the rough surface with CdS nanoparticle
It compares, the surface of CdS/ZIF-8 composite material seems more smooth；Scheme the TEM that c is CdS to scheme；Scheme the TEM that b is CdS/ZIF-8
Figure；It can be found that CdS nanoparticle is uniformly closely coated by ZIF-8 crystal, typical nucleocapsid structure is formd；Scheme d and
Figure e is respectively the more high magnification TEM figure of CdS and CdS/ZIF-8, it can be seen that the ZIF-8 crystal being supported on CdS is transparent
's.Figure g shows the elemental analysis figure of single CdS/ZIF-8 nanoparticle, shows that Cd and S element is mainly distributed on nanoparticle
Center, Zn element is uniformly distributed on entire nanoparticle, further demonstrates the core-shell structure copolymer knot of CdS/ZIF-8 composite material
Structure.
[Fig. 4] is the N of CdS made from CdS/ZIF-8 made from embodiment 1 and comparative example 12Absorption-desorption thermoisopleth pair
Than figure, since the ZIF-8 crystal of load has high porosity, low-density and high-specific surface area, absorption of the CdS/ZIF-8 to nitrogen
It measures more much higher than CdS.
[Fig. 5] is the CO of CdS made from CdS/ZIF-8 made from embodiment 1 and comparative example 12Comparison diagram is adsorbed, is shown
CdS/ZIF-8 is to CO2Adsorption capacity ratio CdS it is strong, be more advantageous to photo catalytic reduction CO2The progress of reaction.
[Fig. 6] figure a is the ultraviolet-visible diffuse reflectance spectrum of CdS, CdS/ZIF-8 and ZIF-8；Figure b reflect CdS and
The forbidden bandwidth of CdS/ZIF-8；Scheming c and figure d is respectively the transient state photoelectricity of CdS and CdS/ZIF-8 at visible light (λ > 420nm)
Stream response.The light absorption of CdS and band structure are influenced less after ZIF-8 in load, and photoelectric current is more stable.
[Fig. 7] is the photo catalytic reduction CO of CdS made from CdS/ZIF-8 made from embodiment 1 and comparative example 12Performance.Figure
A is that CO yield changes with time, and in initial reaction stage, CdS/ZIF-8 shows stronger inertia with respect to CdS, but when with reacting
Between increase, CdS/ZIF-8 shows clear superiority with respect to CdS, and the generating rate of the two CO is respectively 32.13 μm of ol h-1With
26.33μmol h-1, performance boost about 22.03%.Figure b is by-product H2Yield changes with time, the production hydrogen of CdS/ZIF-8
Amount is always below or slightly more than CdS, illustrates that CdS/ZIF-8 has better CO selectivity relative to CdS, available by figure c,
CO of the CdS/ZIF-8 with respect to CdS selectively promotes about 2.39%.Scheme the photo catalytic reduction CO that d is CdS/ZIF-8 and CdS2It follows
Ring performance map, it can be clearly seen that CdS/ZIF-8 shows high stability in cyclic process, and CdS is then with cycle-index
Increase performance obviously decay.
Specific embodiment
Below with reference to specific embodiment, the present invention is further elaborated.Embodiment is interpreted as being merely to illustrate this hair
It is bright rather than limit the scope of the invention.After having read the content of the invention recorded, it is based on the principle of the present invention
The various changes or modification made to the present invention equally fall into claims of the present invention limited range.
Embodiment 1
The preparation of CdS/ZIF-8 and its photo catalytic reduction CO2Performance test
Step (1): the preparation of CdS nanometer material
By 7mmol thiocarbamide, 7mmol Cd (NO3)2·4H2O and 7mmol PVP be dissolved in 70ml ethylene glycol obtain clarifying it is molten
Then mixed solution is transferred in 100ml tetrafluoroethene inner liner stainless steel autoclave, keeps 12h at 120 DEG C by liquid.It will be high
After pressure kettle is cooled to room temperature, a certain amount of methanol is added in acquired solution, CdS nanoparticle is made to be easier to precipitate.By solution from
The heart collects precipitating, washs and be freeze-dried to get the CdS nanoparticle.
Step (2): the preparation of CdS/ZIF-8 composite material
First by 32mg CdS nanoparticle be dispersed in 10ml methanol and ultrasound uniformly, then by 0.2974g Zn
(NO3)2·6H2O is dissolved in 50ml methanol, and the two is mixed while stirring and is continuously stirred at room temperature a period of time, then will
The 2-methylimidazole of 0.3284g is dissolved in 50ml methanol, is added in above-mentioned mixed solution while stirring, equally continues at room temperature
Solution is centrifuged at 1500 rpm after stirring a period of time, precipitating is collected, washs and be freeze-dried to get the CdS/ZIF-8
Composite photocatalyst material.
Step (3): CdS/ZIF-8 composite photocatalyst material photo catalytic reduction CO2Performance test
40mg CdS/ZIF-8 composite photocatalyst material, 200mg is added in the in the mixed solvent that acetonitrile and water form first
2,2'- bipyridyl, 10ml TEOA and 10 μm of ol CoCl2, it is uniformly dispersed, the mixed solution has then been transferred to high quartz thoroughly
In the airproof quartz reactor of lid, and magnetic agitation is carried out, is continually fed into CO in the reaction system2System is existed after 30min
It is closed under one atmospheric pressure carbon dioxide, it is irradiated with xenon lamp from reactor head, control temperature of reaction system is constant 25
DEG C, the gas-phase product in reaction process carries out quantification and qualification by gas-chromatography, and the generating rate of CO is 32.13 μm of ol
h-1, the H of 4h2Yield is about 22.71 μm of ol.
Embodiment 2
The preparation of CdS/ZIF-67 and its photo catalytic reduction CO2Performance test
Step (1): the preparation of CdS nanometer material
By 7mmol thiocarbamide, 7mmol Cd (NO3)2·4H2O and 7mmol PVP be dissolved in 70ml ethylene glycol obtain clarifying it is molten
Then mixed solution is transferred in 100ml tetrafluoroethene inner liner stainless steel autoclave, keeps 12h at 120 DEG C by liquid.It will be high
After pressure kettle is cooled to room temperature, a certain amount of methanol is added in acquired solution, CdS nanoparticle is made to be easier to precipitate.By solution from
The heart collects precipitating, washs and be freeze-dried to get the CdS nanoparticle.
Step (2): the preparation of CdS/ZIF-67 composite material
First by 32mg CdS nanoparticle be dispersed in 10ml methanol and ultrasound uniformly, then by 0.2379g CoCl2·6
(H2O it) is dissolved in 50ml methanol, the two is mixed while stirring and is continuously stirred at room temperature a period of time, then will
The 2-methylimidazole of 0.3284g is dissolved in 50ml methanol, is added in above-mentioned mixed solution while stirring, equally continues at room temperature
Solution is centrifuged at 1500 rpm after stirring a period of time, precipitating is collected, washs and be freeze-dried to get the CdS/ZIF-
67 composite photocatalyst materials.
Step (3): CdS/ZIF-67 composite photocatalyst material photo catalytic reduction CO2Performance test
40mg CdS/ZIF-67 composite photocatalyst material, 200mg is added in the in the mixed solvent that acetonitrile and water form first
2,2'- bipyridyl, 10ml TEOA and 10 μm of ol CoCl2, it is uniformly dispersed, the mixed solution has then been transferred to high quartz thoroughly
In the airproof quartz reactor of lid, and magnetic agitation is carried out, is continually fed into CO in the reaction system2System is existed after 30min
It is closed under one atmospheric pressure carbon dioxide, it is irradiated with xenon lamp from reactor head, control temperature of reaction system is constant 25
DEG C, the gas-phase product in reaction process carries out quantification and qualification by gas-chromatography, and the generating rate of CO is 30.06 μm of ol
h-1, the H of 4h2Yield is about 21.92 μm of ol.
Comparative example 1
The preparation of CdS and its photo catalytic reduction CO2Performance test
Step (1): the preparation of CdS nanometer material
By 7mmol thiocarbamide, 7mmoCd (NO3)2·4H2O and 7mmoPVP is dissolved in 70ml ethylene glycol and obtains clear solution, so
Afterwards, mixed solution is transferred in 100ml tetrafluoroethene inner liner stainless steel autoclave, keeps 12h at 120 DEG C.By autoclave
After being cooled to room temperature, a certain amount of methanol is added in acquired solution, CdS nanoparticle is made to be easier to precipitate.Solution is centrifuged, is received
Collection precipitating, washs and is freeze-dried to get the CdS nanoparticle.
Step (2): the photo catalytic reduction CO of CdS nanoparticle2Performance test
Photo catalytic reduction CO is carried out with the CdS/ZIF-8 composite photocatalyst material in CdS nanoparticle alternative embodiment 12
Performance test, other conditions are same as Example 1.Gas-phase product in reaction process carries out qualitative and quantitative by gas-chromatography
Analysis, the generating rate of CO are 26.33 μm of ol h-1, the H of 4h2Yield is about 21.60 μm of ol.
Comparative example 2
The preparation of ZIF-8 and its photo catalytic reduction CO2Performance test
Step (1): the preparation of ZIF-8
By 1.1896g Zn (NO3)2·6H2O is dissolved in 50ml methanol, is then dissolved in the 2-methylimidazole of 1.3136g
The two is mixed while stirring and is continuously stirred at room temperature a period of time, precipitating is collected by centrifugation, washs and freezes by 50ml methanol
Drying is to get the ZIF-8 nanocrystal.
Step (2): ZIF-8 nanocrystal photo catalytic reduction CO2Performance test
Photo catalytic reduction is carried out with the CdS/ZIF-8 composite photocatalyst material in ZIF-8 nanocrystal alternative embodiment 1
CO2Performance test, other conditions are same as Example 1.Gas-phase product in reaction process by gas-chromatography carry out it is qualitative with
Quantitative analysis, without CO and H2It generates.
Claims (10)
1. a kind of CdS/ metal organic frame composite photocatalyst material, it is characterised in that: modified by metal organic frame and received in CdS
Rice corpuscles surface is constituted.
2. CdS/ metal organic frame composite photocatalyst material according to claim 1, it is characterised in that: the metal has
Machine frame is ZIF-8.
3. the preparation method of CdS/ metal organic frame composite photocatalyst material of any of claims 1 or 2, it is characterised in that:
Using thiocarbamide and cadmium salt as raw material, received by solvent structure CdS nanoparticle, then by heterogeneous sedimentation in situ in CdS
Rice corpuscles surface modification metal organic frame is to get CdS/ metal organic frame composite photocatalyst material.
4. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 3, it is characterised in that:
Solvent thermal reaction will be carried out to get CdS nanoparticle containing the organic solution of thiocarbamide, cadmium salt and dispersing agent.
5. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 4, it is characterised in that:
The molar ratio of thiocarbamide and cadmium salt is 0.2:1~5:1；
The molar ratio of thiocarbamide and dispersing agent is 0.5:1~3:1；The dispersing agent is PVP；
Solvent is ethylene glycol in organic solution.
6. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 4 or 5, feature exist
It is 100~180 DEG C in: the temperature of the solvent thermal reaction, the time is 4~for 24 hours.
7. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 3, it is characterised in that:
In CdS nanoparticle dispersion liquid, sequentially adds metal salt solution and organic ligand solution is stirred to react, be centrifuged after the reaction was completed
Separation is to get CdS/ metal organic frame composite photocatalyst material.
8. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 7, it is characterised in that:
The volume ratio of CdS nanoparticle dispersion liquid and metal salt solution and organic ligand solution is 5~100:20~500:20~500；
The concentration of the CdS nanoparticle dispersion liquid is 1~20mg/mL；The concentration of the metal salt solution is 5~100mM；It is described to have
The concentration of machine ligand solution is 5~400mM；The CdS nanoparticle dispersion liquid is using methanol as solvent；The metal salt is molten
Liquid is zinc salt methanol solution；The organic ligand solution is 2-methylimidazole methanol solution.
9. the preparation method of CdS/ metal organic frame composite photocatalyst material according to claim 7, it is characterised in that:
It is 0.5~3h that the time being stirred to react after metal salt solution, which is added, and it is 0.5 that the time being stirred to react after organic ligand solution, which is added,
~6h.
10. a kind of application of CdS/ metal organic frame composite photocatalyst material of any of claims 1 or 2, it is characterised in that:
Applied to photocatalytic reduction of carbon oxide.
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| CN115532321B (en) * | 2022-11-03 | 2023-09-05 | 北京工业大学 | High-efficiency multichannel composite photocatalyst based on metal-organic framework material and preparation method thereof |
| CN116535657A (en) * | 2023-04-06 | 2023-08-04 | 中南大学 | In-situ modified MOF material, preparation method thereof and application of in-situ modified MOF material as photocatalyst |
| CN116535657B (en) * | 2023-04-06 | 2024-04-23 | 中南大学 | In-situ modified MOF material, preparation method thereof and application of in-situ modified MOF material as photocatalyst |
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