CN106311294B - A method of zinc phosphide/phosphatization cobalt heterojunction photocatalyst is constructed based on MOFs templates - Google Patents
A method of zinc phosphide/phosphatization cobalt heterojunction photocatalyst is constructed based on MOFs templates Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 17
- 239000006011 Zinc phosphide Substances 0.000 title claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 10
- 239000010941 cobalt Substances 0.000 title claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 10
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 10
- 229940048462 zinc phosphide Drugs 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000001782 photodegradation Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000008614 2-methylimidazoles Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 2
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A method of zinc phosphide/phosphatization cobalt heterojunction photocatalyst is constructed based on MOFs templates, belongs to the technical field of catalysis material preparation.Using ZIF ZnCo as template, constructed with porous structure zinc phosphide/phosphatization cobalt hetero-junctions catalyst by carrying out oxidation and phosphorating treatment to it.The original skeleton structure features of presoma MOFs are maintained based on the catalyst, active catalyst sites fully expose, the catalyst promotes the separation of photo-generate electron-hole by good synergistic effect and improves photoresponse behavior simultaneously, therefore shows excellent photodegradation water hydrogen manufacturing performance.
Description
Technical field
The invention belongs to technical field prepared by catalysis material, technology is related to metal-organic framework materials (Metal-
Organic frameworks, MOFs) and its derivative preparation method, being based particularly on bimetallic MOFs, to construct phosphide different
Matter knot photocatalyst material.
Background technology
Currently, with various rings caused by the consumption aggravation of the non-renewable resources such as coal, oil, natural gas and energy consumption
Border pollution problem also getting worse, therefore develop new cleaning fuel and become the hot spot of people's common concern.It is new in exploitation cleaning
In energy technology field, solar energy abundant on the earth is developed and used by Photocatalitic Technique of Semiconductor and is converted into cleaning
The energy is considered as one of the effective way for solving energy crisis and problem of environmental pollution.Wherein, heterojunction semiconductor photocatalysis
Agent has special band structure and carrier transport characteristic, can effectively inhibit the compound of light induced electron and hole, to carry
High-quantum efficiency, therefore as the research hotspot of conductor photocatalysis hydrogen preparation field.But the energy band of heterojunction semiconductor catalyst
Structure is adjusted still is faced with many challenges with synthetic method, and this is mainly due to two or more position of energy band is matched
The compound method used of semi-conducting material is usually complicated cumbersome, it is difficult to effectively compound by easy method.Therefore, how to open
It sends out the heterojunction photocatalysis material of structure novel and improves its photocatalysis performance as one of people's urgent problem to be solved.
MOFs is a kind of novel porous materials, it be by metal ion or ion cluster and nitrogenous, oxygen etc. organic ligand from
What is assembled possesses the material of special pore passage structure.MOFs is in adsorbing separation, gas storage, medicament slow release, gas at present
The various fields such as storage have potential application.In recent years, the new function based on MOFs templated synthesis specific structures
Material is by the extensive concern of researcher.Nevertheless, about the basic theory understanding to MOFs derivative catalysts
Still there are many problems in terms of photocatalysis performance Investigation on intensification.Main cause is the MOFs derivative catalysts of forefathers' report
Structure composition is single, and many derivative catalysts light absorption utilization rate during light-catalyzed reaction is relatively low, and photocatalysis performance is difficult
To be promoted.In addition, the report about the MOFs heterojunction photocatalysts constructed still is rarely reported, therefore how to obtain electronics sky
Cave separating capacity is strong, light abstraction width is wide, stability is good and has the MOFs derivatives photochemical catalyst of practical application potentiality still
It is faced with lot of challenges.
Invention content
The object of the present invention is to provide one kind with bimetallic zinc cobalt MOFs (Zeolitic imidazolate
Frameworks, ZIF-ZnCo) it is that construct porous structure zinc phosphide/phosphatization cobalt with excellent Photocatalyzed Hydrogen Production performance different for template
The method of matter knot material.
It mainly includes the following steps that：
(1) synthesis of ZIF-ZnCo:It is stirred at room temperature under state, by 2-methylimidazole, cabaltous nitrate hexahydrate and six hydrations
Zinc nitrate is dissolved in methanol, is stored at room temperature 12~36h, is washed, activated with methanol after mixed liquor centrifugation, be dried in vacuo, obtain ZIF-
ZnCo；
(2)ZnO/Co3O4Preparation：ZIF-ZnCo obtained by step (1) is placed in mortar and is ground, under air conditions, with 2
The heating rate of~5 DEG C/min is warming up to 300~400 DEG C of 2~5h of roasting, obtains ZnO/Co3O4；
(3)Zn3P2The preparation of/CoP：By NaH2PO2·H2O, ZnO/Co obtained by step (2)3O4It is placed in mortar and grinds
10min under the conditions of nitrogen protection, is warming up to 250~350 DEG C of 0.5~4h of phosphatization with the heating rate of 2~5 DEG C/min, waits for temperature
Room temperature is dropped to, products therefrom deionized water and absolute ethyl alcohol are washed, are dried in vacuo, and obtain Zn3P2/CoP。
The molar ratio of 2-methylimidazole, cabaltous nitrate hexahydrate and zinc nitrate hexahydrate is preferably 40 in step (1):9:9, room
Warm time of repose is 12~36h.
Calcination temperature is 300~400 DEG C in step (2), and roasting time is 2~5h.
Phosphatization temperature is 250~350 DEG C in step (3), and phosphating time is 0.5~4h.
For the present invention using bimetallic ZIF-ZnCo as template, having been constructed by oxidation and further phosphorating treatment has excellent light
It is catalyzed porous structure zinc phosphide/phosphatization cobalt hetero-junctions catalyst of H2-producing capacity.Porous structure zinc phosphide/phosphatization cobalt hetero-junctions material
Material is the polyhedral structure that side is relatively protruded.The polyhedron length of side is in 100nm or so；Preparation method of the present invention is simple, is easy to
Implement.The derivative photochemical catalyst of preparation maintains the original skeleton structure features of presoma MOFs, and active catalyst sites are abundant
Exposure.The composite catalyst constructed simultaneously promotes the separation of photo-generate electron-hole by good synergistic effect and improves light
Respondent behavior, therefore show excellent photodegradation water hydrogen manufacturing performance.
Description of the drawings
Fig. 1 is the scanning electron microscope schematic diagram of ZIF-ZnCo in present example.
Fig. 2 is ZnO/Co in present example3O4Scanning electron microscope schematic diagram.
Fig. 3 is Zn in present example3P2The scanning electron microscope schematic diagram of/CoP.
Fig. 4 is Zn in present example3P2The photodegradation water hydrogen manufacturing performance figure of/CoP.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
The first step：Be stirred at room temperature under state, weigh 0.656g 2-methylimidazoles, 0.249g cabaltous nitrate hexahydrates and
0.257g zinc nitrate hexahydrates are dissolved in 50mL methanol, are stored at room temperature for 24 hours, are washed, are activated, 60 DEG C with methanol after mixed liquor centrifugation
Lower vacuum drying 8h, obtains ZIF-ZnCo.
Second step：The ZIF-ZnCo prepared in 100mg step 1 is weighed to be placed in mortar and grind 5min, under air conditions,
300 DEG C of roasting 3h are warming up to the heating rate of 2 DEG C/min, obtain ZnO/Co3O4。
Third walks：Weigh the ZnO/Co prepared in 25mg step 23O4、0.6603gNaH2PO2·H2O is placed in mortar and grinds
10min is ground, under the conditions of nitrogen protection, 250 DEG C of phosphatization 2h is warming up to the heating rate of 2 DEG C/min, wait for that temperature drops to room temperature, institute
It obtains product deionized water and absolute ethyl alcohol washs, is dried in vacuo 8h at 60 DEG C, obtain Zn3P2/CoP。
Embodiment 2
The first step：Be stirred at room temperature under state, weigh 0.656g 2-methylimidazoles, 0.249g cabaltous nitrate hexahydrates and
0.257g zinc nitrate hexahydrates are dissolved in 50mL methanol, are stored at room temperature for 24 hours, are washed, are activated, 60 DEG C with methanol after mixed liquor centrifugation
Lower vacuum drying 8h, obtains ZIF-ZnCo；
Second step：The ZIF-ZnCo prepared in 100mg step 1 is weighed to be placed in mortar and grind 5min, under air conditions,
400 DEG C of roasting 2h are warming up to the heating rate of 2 DEG C/min, obtain ZnO/Co3O4；
Third walks：Weigh the ZnO/Co prepared in 25mg step 23O4、0.7000gNaH2PO2·H2O is placed in mortar and grinds
10min is ground, under the conditions of nitrogen protection, 300 DEG C of phosphatization 1h is warming up to the heating rate of 2 DEG C/min, wait for that temperature drops to room temperature, institute
It obtains product deionized water and absolute ethyl alcohol washs, is dried in vacuo 8h at 60 DEG C, obtain Zn3P2/CoP；
The test result of material obtained by above-described embodiment is identical, specifically sees below：
(1) material morphology characterizes：
Select Hitachi S-3400 models field emission scanning electron microscope respectively to ZIF-ZnCo, ZnO/Co3O4And Zn3P2/
CoP carries out structure and morphology characterization, sees Fig. 1, Fig. 2 and Fig. 3 respectively.Fig. 1 is presoma ZIF-ZnCo, Fig. 2 ZnO/Co3O4, Fig. 3
For heterojunction photocatalyst Zn3P2/CoP。
(2) material light catalysis H2-producing capacity characterizes：
Heterojunction photocatalyst Zn as can be seen from Figure 43P2/ CoP ratios Zn3P2There is superior photocatalysis performance with CoP.
The above is the preferred embodiments of the present invention, but the present invention should not be limited to the example disclosure.Institute
The lower equivalent or modification completed of spirit disclosed in this invention is not departed from all, both falls within the scope of protection of the invention.
Claims (3)
1. a kind of method for constructing zinc phosphide/phosphatization cobalt heterojunction photocatalyst based on MOFs templates, which is characterized in that including with
Lower step：
(1) synthesis of ZIF-ZnCo:It is stirred at room temperature under state, by 2-methylimidazole, cabaltous nitrate hexahydrate and six nitric hydrates
Zinc is dissolved in methanol, is stored at room temperature 12~36h, is washed, activated with methanol after mixed liquor centrifugation, be dried in vacuo, obtain ZIF-ZnCo；
(2)ZnO/Co3O4Preparation：ZIF-ZnCo obtained by step (1) is placed in mortar and is ground, under air conditions, with 2~5
DEG C/heating rate of min is warming up to 300~400 DEG C of 2~5h of roasting, obtain ZnO/Co3O4；
(3)Zn3P2The preparation of/CoP：By NaH2PO2·H2O, ZnO/Co obtained by step (2)3O4It is placed in mortar and grinds 10min, nitrogen
Under the conditions of gas shielded, 250~350 DEG C of 0.5~4h of phosphatization are warming up to the heating rate of 2~5 DEG C/min, wait for that temperature drops to room
Temperature, products therefrom deionized water and absolute ethyl alcohol are washed, are dried in vacuo, and obtain Zn3P2/CoP；
The molar ratio of 2-methylimidazole, cabaltous nitrate hexahydrate and zinc nitrate hexahydrate is 40 in step (1):9:9.
2. the zinc phosphide being prepared according to the method for claim 1/phosphatization cobalt heterojunction photocatalyst.
3. the purposes of the zinc phosphide being prepared according to the method for claim 1/phosphatization cobalt heterojunction photocatalyst, special
Sign is, is used for photodegradation water hydrogen manufacturing.
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| CN109806888B (en) * | 2019-02-23 | 2021-03-30 | 华南理工大学 | 1T-MoS2Modified ZnCoS solid solution hollow dodecahedron nanocomposite and preparation method and application thereof |
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| CN111250137A (en) * | 2020-02-20 | 2020-06-09 | 肇庆市华师大光电产业研究院 | Modified g-C for photocatalytic hydrogen production3N4Process for preparing catalyst |
| CN112808238B (en) * | 2020-12-31 | 2022-04-22 | 华南理工大学 | Inorganic semiconductor-MOFs derivative double-cavity composite material and preparation method thereof |
| CN112675831A (en) * | 2021-01-04 | 2021-04-20 | 江苏大学 | Preparation method of MOF-derived zinc oxide composite titanium dioxide heterojunction and application of heterojunction in photoelectric water decomposition |
| CN113562775B (en) * | 2021-08-30 | 2023-06-30 | 杭州恒毅智创科技有限公司 | Preparation method of zinc oxide/cobaltosic oxide hollow cube nanomaterial |
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| CN103230777A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Large-scale adsorbing material ZIF-8 preparation method and forming method |
| CN104803365A (en) * | 2015-05-07 | 2015-07-29 | 陕西科技大学 | Preparation method of cobalt phosphide three-dimensional sheet flower |
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