CN111760582A - MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst - Google Patents
MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst Download PDFInfo
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- CN111760582A CN111760582A CN202010448504.5A CN202010448504A CN111760582A CN 111760582 A CN111760582 A CN 111760582A CN 202010448504 A CN202010448504 A CN 202010448504A CN 111760582 A CN111760582 A CN 111760582A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 37
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 8
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 10
- 229960002989 glutamic acid Drugs 0.000 claims description 10
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000002091 nanocage Substances 0.000 claims 2
- 239000013384 organic framework Substances 0.000 claims 1
- 239000011550 stock solution Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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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
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to a MOF-based MoP-Cu3A P transition metal phosphide heterojunction photocatalyst and a preparation method thereof are provided, the MOF-based MoP-Cu3P transition metal phosphide heterojunction catalyst is prepared by a one-step method, MOF is a metal organic framework material, and a derivative of MOF is adopted as a precursor to prepare highly dispersed MOF-based MoP-Cu3P transition metal phosphide nano-material. MoP-Cu3The P transition metal phosphide composite material is synthesized by reacting derivatives of MOF with sodium dihydrogen phosphate at high temperature, and utilizes the high metal conductivity and good H of the MoP+Transfer capability, excellent activity as a promoter to enhance and absorb and accelerate semiconductor carrier separation to improve hydrogen evolution efficiency, Cu3P has good photoelectric property and is compounded with MoP metal phosphide, so that the problem of serious reduction of hydrogen evolution conversion efficiency caused by carrier recombination is solved; using MoP and Cu3The close contact between P will establish Schottky junction to accelerate the carrierSeparation and transfer.
Description
Technical Field
The invention belongs to the field of environment-friendly photocatalytic hydrogen production, and particularly relates to MOF-based MoP-Cu3A P transition metal phosphide heterojunction photocatalyst.
Background
Excessive consumption of fossil fuels poses a series of energy and environmental problems, and hydrogen, a clean renewable energy source with high calorific value, will likely replace fossil fuels. Photocatalytic water splitting is considered to be the most promising method for obtaining hydrogen, and to date, many effective photocatalysts have been developed with important roles. Wherein the transition metal phosphide has good electrical conductivity and excellent catalytic activity, has been proven to be an excellent catalyst for Hydrogen Evolution Reaction (HER), such as Ni2P，CoP，Co2P， FeP，Cu3P, WP and MoP. Wherein, Cu3P has good photoelectric property and abundant resources, and has great research and development value when being used as a catalyst material for photocatalytic water decomposition. However, it also has some limitations, e.g. pure Cu3P usually exhibits severe carrier recombination, which has a severe effect on photocatalytic activity. Pure Cu3The poor photocatalytic performance of P has prompted the development of appropriate strategies to improve its photocatalytic performance. Numerous studies have demonstrated that the construction of heterojunctions is a universally effective method for inducing carrier separation and migration.
In the prior art, for example, a chinese patent with an issued publication number of CN 108452817B discloses a supported transition metal phosphide and a preparation method thereof, wherein the supported transition metal phosphide does not need to introduce other chemical substances as a phosphorus source and prepare a template in the preparation process, but utilizes a phosphorus element contained in a biomass material as the phosphorus source to generate the transition metal phosphide in situ. The biomass material, which is a source of the biomass material, contains a large amount of elements such as carbon, hydrogen, oxygen, nitrogen, phosphorus and the like; through a simple hydrothermal method, the biological material can form a carbon material with a large number of pores and high electric conductivity after carbonization; and the surface of the biomass material has abundant surface functional groups, so that the biomass material has strong capability of adsorbing and reducing high-valence metal ions, but the purification and preparation of a phosphorus source needs to consume part of the phosphorus source more than the capacity, and the biomass material is not beneficial to industrial production.
The prior art, such as the Chinese patent with the publication number of CN 106694004B, discloses a supported transition metal phosphide catalyst and a preparation method thereof, belonging to the field of transition metal phosphide. The catalyst is prepared by adopting a coprecipitation-temperature programming reduction method, and the method comprises the following steps: the supported transition metal phosphide catalyst is prepared by synthesizing a layered composite hydroxide precursor which takes composite hydroxide of metal cations such as magnesium, aluminum and transition metal as a main layer plate and anions such as hydrogen phosphate as an intercalation by a coprecipitation method, carrying out roasting thermal decomposition to obtain uniform mixed oxide with high specific surface area, and then carrying out hydrogen programmed temperature rise reduction. The raw materials are common inorganic reagents, the price is low, the safety and the pollution are avoided, and the method can be used for preparing various supported transition metal phosphide catalysts such as iron phosphide, cobalt phosphide, nickel phosphide and the like.
However, the prior art is based on Cu3The synthesis of the P catalyst is relatively complex, and the preparation method is limited, so that the photoelectric conversion efficiency of the P catalyst cannot be effectively improved.
Disclosure of Invention
Aiming at the problems of low hydrogen evolution efficiency and carrier recombination in the single catalyst catalysis process of the existing hydrogen evolution photocatalyst, the invention provides a MOF-based MoP-Cu with simple and convenient operation and high hydrogen evolution rate3A P transition metal phosphide heterojunction photocatalyst.
The technical scheme adopted by the invention for realizing the purpose is as follows:
preparing MOF-based MoP-Cu3P transition metal phosphide heterojunction catalyst by one-step method, wherein MOF is metal organic framework material, and preparing highly dispersed MOF-based MoP-Cu by taking derivative of MOF as precursor3P transition metal phosphide nano-material. MoP-Cu3The P transition metal phosphide composite material is synthesized by reacting derivatives of MOF with sodium dihydrogen phosphate at high temperature, and utilizes the high metal conductivity and good H of the MoP+Transfer capability, excellent activity as a promoter to enhance and absorb and accelerate semiconductor carrier separation to improve hydrogen evolution efficiency, Cu3P has good photoelectric property and is compounded with MoP metal phosphide, so that the problem of serious reduction of hydrogen evolution conversion efficiency caused by carrier recombination is solved; using MoP and Cu3The close contact between P will create a schottky junction, accelerating the separation and transfer of carriers.
Preferably, the derivative of MOF is: NENU-5 (a MOF derivative containing Cu and Mo), HKUST-1 (a MOF derivative containing only Cu). Cu in NENU-5, HKUST-12+Not only acts as a copper source, but also is combined with organic ligands of MOF derivatives to form octahedrons to strengthen MoP-Cu3P binding ability, effective extension of MoP-Cu3The service life of P.
Preferably, the MoP-Cu3P is a transition metal phosphide composite material, and the precursor is as follows: phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate(Cu2+) L-glutamic acid, wherein phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate (Cu)2+) The mass percentage of the L-glutamic acid is as follows: 10-20%, 20-35%, 45-70%. PMo phosphomolybdic acid12Is a polyoxometallate, mainly provides a molybdenum source, and is packaged in Cu3P octahedron inside the cavity.
Preferably, the preparation solution of the precursor of the MoP-Cu3P hybrid has a pH of 3, is pre-acidified and is subjected to a pre-acidification treatment in H+At a higher concentration, Cu is promoted2+To MoP-Cu3And (4) converting P.
The invention also provides MOF-based MoP-Cu3The preparation method of the P transition metal phosphide heterojunction photocatalyst comprises the following steps:
1) phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate (Cu)2+) And L-glutamic acid is dissolved in 50mL of deionized water, and the mixture is stirred for 1 to 3 hours at room temperature to obtain a clear solution.
2) Dissolving 1,3, 5-benzene tricarboxylic acid (BTC) in ethanol, and stirring for 1-3h at room temperature to obtain a clear solution.
3) Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 14-28 h;
4) centrifuging the product obtained in the step 3), washing with ethanol for 3 times, washing with deionized water for 1 time, and drying the precipitate to obtain a MOFNENU-5 derivative;
5) placing the product of the step 4) at the outlet end of a double-temperature-zone tubular furnace, placing sodium dihydrogen phosphate at the inlet end, pumping the pressure of the tubular furnace to 100Pa, introducing Ar gas, and carrying out high-temperature synthesis reaction;
preferably, in the two-temperature zone tubular furnace, Ar gas is introduced at a rate of 80 s.c.c.m.1 h before the reaction.
Preferably, the temperature of the gas inlet end of the two-temperature zone tubular furnace is increased to 100 ℃ within 20 minutes, the temperature is maintained for 30 minutes, the temperature is increased to 200 ℃ within 20 minutes, the temperature is maintained for 30 minutes, the temperature is decreased to 150 ℃ within 20 minutes, the temperature is maintained for 30 minutes, and then the temperature is cooled to the room temperature.
Compared with the prior art, the invention has the following advantages:
1) the derivative of MOF is selected from NENU-5 (also a MOF derivative of Cu and Mo) and HKUST-1 (only a MOF derivative of Cu), and the prepared MoP-Cu3P has higher photocatalytic activity and outstanding structural stability compared with a single catalyst.
2) The close contact between the MoP and the Cu3P establishes a Schottky junction, accelerates the separation and transfer of carriers and improves the hydrogen evolution efficiency;
3) the dual-zone tube furnace is synchronously regulated and controlled in a non-isothermal way, and the prepared MOFs composite MoP-Cu3P transition metal phosphide heterojunction catalyst has a stable octahedral structure, so that the service life of the catalyst is prolonged;
4)Cu2+not only acts as a copper source, but also combines with organic ligands of MOF derivatives to form octahedrons, and constructs the stable MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst.
5) The MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst is prepared by a one-step method, and the method is simple and controllable and is easy to popularize.
Drawings
FIG. 1 is a scanning electron microscope image of a MOFs-based MoP-Cu3P composite material;
FIG. 2 is a hydrogen production diagram of MoP, CuP3, MoP/CuP3 and MOFs-based MoP-Cu3P catalysts;
FIG. 3 is a diagram of hydrogen production rates of MoP, CuP3, MoP/CuP3 and MOFs-based MoP-Cu3P catalysts;
FIG. 4 is a graph of photocurrent density versus time under visible light for MoP, CuP3, MOFs based MoP-Cu3P catalysts.
Detailed Description
For further understanding of the contents, features and effects of the present invention, the following examples are given, but the preparation scheme of the present invention is not limited to these examples, and the following detailed descriptions are given:
example 1:
1) 3.2g of copper acetate monohydrate (Cu)2+) And 4.8g of L-glutamic acid were dissolved in 50mL of deionized water and stirred at room temperature for 3 hours to obtain a clear solution.
2) 2.5g of 1,3, 5-benzenetricarboxylic acid (BTC) was dissolved in 50mL of ethanol and stirred at room temperature for 3 hours to obtain a clear solution.
3) Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 28 h;
4) centrifuging the product obtained in step 3), washing with ethanol for 3 times, washing with Deionized (DI) water for 1 time, and drying the precipitate to obtain the MOFNENU-5 derivative.
5) And 4) placing the product in the outlet end of a double-temperature-zone tubular furnace, placing 4.6g of sodium dihydrogen phosphate in the inlet end, pumping the air pressure of the tubular furnace to 100Pa, introducing Ar gas, heating the inlet end to 300 ℃, heating the outlet end to 680 ℃, and reacting for 1-3h to obtain the MoP transition metal phosphide photocatalyst.
And (3) carrying out a hydrogen evolution test on the product obtained in the step (5), wherein the test conditions are as follows: UV-visible spectrophotometer (Perkin-Elmer Lambda 35 UV-VIS-NIR).
Example 2:
1) 3.2g of copper acetate monohydrate (Cu)2+) And 4.8g of L-glutamic acid were dissolved in 50mL of deionized water and stirred at room temperature for 3 hours to obtain a clear solution.
2) 2.5g of 1,3, 5-benzenetricarboxylic acid (BTC) was dissolved in 50mL of ethanol and stirred at room temperature for 3 hours to obtain a clear solution.
3) Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 28 h;
4) centrifuging the product obtained in step 3), washing with ethanol for 3 times, washing with Deionized (DI) water for 1 time, and drying the precipitate to obtain the MOFNENU-5 derivative.
5) Putting the product obtained in the step 4) at the outlet end of a double-temperature-zone tubular furnace, putting 4.6g of sodium dihydrogen phosphate at the inlet end of the double-temperature-zone tubular furnace, pumping the air pressure of the tubular furnace to 100Pa, introducing Ar gas, raising the temperature of the inlet end of the double-temperature-zone tubular furnace to 100 ℃ within 20 minutes, preserving the heat for 30 minutes, raising the temperature to 200 ℃ within 20 minutes, preserving the heat for 30 minutes, reducing the temperature to 150 ℃ within 20 minutes, preserving the heat for 30 minutes, and cooling to room temperature to obtain CuP3A transition metal phosphide photocatalyst.
6) And (3) carrying out a hydrogen evolution test on the product obtained in the step (5), wherein the test conditions are as follows: UV-visible spectrophotometer (Perkin-Elmer Lambda 35 UV-VIS-NIR).
Example 3:
1) 3.2g of phosphomolybdic acid hydrate (PMo12), 3.2g of copper acetate monohydrate (Cu)2+) And 4.8g of L-glutamic acid in 50mL of deionized water were stirred at room temperature for 3 hours to obtain a clear solution.
2) 2.5g of 1,3, 5-benzenetricarboxylic acid (BTC) was dissolved in 50mL of ethanol and stirred at room temperature for 3 hours to obtain a clear solution.
3) Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 28 h;
4) centrifuging the product obtained in the step 3), washing with ethanol for 3 times, washing with Deionized (DI) water for 1 time, and drying the precipitate to obtain the MOF NENU-5 derivative.
5) Grinding and mixing the product obtained in the step 4) and 4.6g of sodium dihydrogen phosphate, synthesizing at a high temperature under the air pressure of 100Pa, heating the air inlet end of the double-temperature-zone tubular furnace to 80 ℃ within 20 minutes, preserving heat for 30 minutes, heating to 150 ℃ within 20 minutes, preserving heat for 30 minutes, cooling to 130 ℃ within 20 minutes, preserving heat for 30 minutes, and cooling to room temperature to obtain the MOF-based MoP/Cu3P transition metal phosphide heterojunction catalyst
6) And (3) carrying out a hydrogen evolution test on the product obtained in the step (5), wherein the test conditions are as follows: UV-visible spectrophotometer (Perkin-Elmer Lambda 35 UV-VIS-NIR).
Example 4:
1) 3.2g of phosphomolybdic acid hydrate (PMo12), 3.2g of copper acetate monohydrate (Cu)2+) And 4.8g of L-glutamic acid dissolved in 50mL of deionized water is dissolved in 50mL of deionized water, and the mixture is stirred at room temperature for 1 to 3 hours to obtain a clear solution.
2) Dissolving a certain mass of 1,3, 5-benzene tricarboxylic acid (BTC) in 50mL of ethanol, and stirring for 1-3h at room temperature to obtain a clear solution.
3) Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 14-28 h;
4) centrifuging the product obtained in the step 3), washing with ethanol for 3 times, washing with Deionized (DI) water for 1 time, and drying the precipitate to obtain the MOF NENU-5 derivative.
5) And 4) placing the product at the outlet end of the double-temperature-zone tubular furnace, placing sodium dihydrogen phosphate with certain mass at the inlet end, heating the inlet end of the double-temperature-zone tubular furnace to 100 ℃ within 20 minutes, preserving heat for 30 minutes, heating to 200 ℃ within 20 minutes, preserving heat for 30 minutes, cooling to 150 ℃ within 20 minutes, preserving heat for 30 minutes, and cooling to room temperature to obtain the MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst.
6) Carrying out a hydrogen evolution test on the product obtained in the step 5), wherein the test conditions are as follows: UV-visible spectrophotometer (Perkin-Elmer Lambda 35 UV-VIS-NIR).
7) And (5) carrying out scanning electron microscope testing on the product obtained in the step 5) and drawing.
FIG. 1 is an SEM image of a MoP-Cu3P hybrid, and it can be seen that the structure remains unchanged and remains octahedral after the phosphorization of MoP-Cu 3P. MoP-Cu3P and NENU-5 have similar specific surface areas and porous structures. Two different lattice fringes can be observed at the boundary, indicating an interface with close contact between MoP and Cu3P, indicating that a schottky structure is established with MoP-Cu 3P.
In FIGS. 2 and 3, it can be seen that in the first cycle of 350 minutes, the hydrogen yield of pure Cu3P was 1494. mu. mol/g, the photocatalytic activity of MoP was also measured under the same conditions, and no significant H was observed2In comparison with the physical mixture of Cu3P and MoP, the MoP-Cu3P hybrid showed enhanced photocatalytic activity, and the hydrogen yield of the MoP-Cu3P hybrid was increased to 4988. mu. mol/g. In addition, the sample obtained still maintained excellent photocatalytic activity after four consecutive cycles, and the hydrogen yield was about 4788. mu. mol/g (4% decay), indicating that the material had excellent cycling stability.
FIG. 4 is a graph of photocurrent density-time curve under visible light of MoP, CuP3 and MOFs-based MoP-Cu3P catalysts, and the photocurrent density of the MoP-Cu3P hybrid is 2.7mA/cm2While the photocurrent density of pure Cu3P was 0.97mA/cm2. The MoP almost photocurrent density is almost zero. The photocurrent density of the MoP 3P hybrid was higher than that of the other two monomers, indicating that the MoP 3P hybrid can effectively reduce hydrogen evolution from water. In addition, there was no photocurrent density decay with increasing cycling period, which means that the samples had good cycling stabilityAnd (4) sex.
Although embodiments of the present invention have been described in detail, it will be appreciated by those skilled in the art that a wide variety of changes, modifications, substitutions, and alterations can be made herein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst, characterized in that the MOF group MoP-Cu3P is a molecular cage structure, and the cage is Cu3P composition, Cu3P molecular cage wraps MOP, and the MOF group MoP-Cu3The precursor of P is a derivative of a metal organic framework material, and the precursor organic framework derivative is subjected to pre-acidification treatment.
2. The MOF-based MoP-Cu of claim 13The P transition metal phosphide heterojunction photocatalyst is characterized in that the derivative of the MOF is as follows: NENU-5 (a MOF derivative containing Cu and Mo), HKUST-1 (a MOF derivative containing only Cu).
3. The MOF-based MoP-Cu of claim 13P transition metal phosphide heterojunction photocatalyst, characterized in that, the MoP-Cu3P is a transition metal phosphide composite material, and the precursor is as follows: phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate (Cu)2+) L-glutamic acid, wherein phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate (Cu)2+) The mass percentage of the L-glutamic acid is as follows: 10-20%, 20-35%, 45-70%. PMo phosphomolybdic acid12Is a polyoxometallate, mainly provides a molybdenum source, and is packaged in Cu3P octahedron inside the cavity.
4. The MOF-based MoP-Cu of claim 13A P-transition metal phosphide heterojunction photocatalyst characterized in that: preparation of the precursor of the MoP-Cu3P hybridThe stock solution had a pH of 3.
5. The MOF-based MoP-Cu of claim 13A preparation method of a P transition metal phosphide heterojunction photocatalyst,
the specific method comprises the following steps:
1) phosphomolybdic acid hydrate (PMo)12) Copper acetate monohydrate (Cu)2+) Dissolving L-glutamic acid in 50mL of deionized water, and stirring at room temperature for 1-3h to obtain a clear solution;
2) dissolving 1,3, 5-benzene tricarboxylic acid (BTC) in ethanol, and stirring for 1-3h at room temperature to obtain a clear solution.
Adding the solution of step 2) into the clear solution A of step 1) and stirring vigorously for 14-28 h;
3) centrifuging the product obtained in the step 3), washing with ethanol for 3 times, washing with deionized water for 1 time, and drying the precipitate to obtain MOF NENU-5 derivatives;
4) and 4) placing the product at the outlet end of the double-temperature-zone tubular furnace, placing sodium dihydrogen phosphate at the inlet end, pumping the pressure of the tubular furnace to 100Pa, introducing Ar gas, and carrying out high-temperature synthesis reaction.
6. The MOF-based MoP-Cu of claim 53The preparation method of the P transition metal phosphide heterojunction photocatalyst is characterized in that Ar gas is introduced into the double-temperature-zone tubular furnace 1h before the reaction, and the speed is 80 s.c.c.m.
7. The MOF-based MoP-Cu of claim 53The preparation method of the P transition metal phosphide heterojunction photocatalyst is characterized in that in the step 4), the temperature of the gas inlet end of the double-temperature-zone tubular furnace is increased to 80-100 ℃ within 20 minutes, the temperature is maintained for 30 minutes, the temperature is increased to 150-200 ℃ within 20 minutes, the temperature is maintained for 30 minutes, the temperature is decreased to 130-150 ℃ within 20 minutes, the temperature is maintained for 30 minutes, and then the temperature is cooled to room temperature.
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| CN114232021A (en) * | 2021-11-24 | 2022-03-25 | 黑龙江大学 | Preparation method of molybdenum phosphide nano microsphere composite material |
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| CN114232021A (en) * | 2021-11-24 | 2022-03-25 | 黑龙江大学 | Preparation method of molybdenum phosphide nano microsphere composite material |
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