CN116870970A - Z-type heterojunction CuInS 2 Cu-MOF composite material and preparation method and application thereof - Google Patents
Z-type heterojunction CuInS 2 Cu-MOF composite material and preparation method and application thereof Download PDFInfo
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- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 238000000034 method Methods 0.000 claims abstract description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
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- 229940045803 cuprous chloride Drugs 0.000 claims description 12
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 9
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- 239000003054 catalyst Substances 0.000 claims description 7
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- 239000002105 nanoparticle Substances 0.000 claims description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
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- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 21
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- 239000012621 metal-organic framework Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 238000007146 photocatalysis Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 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
- 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
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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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Abstract
The invention belongs to the technical field of nano-composite, and in particular relates to a Z-type heterojunction CuInS 2 Cu-MOF composite material, and its preparation method and application are provided. The invention adopts a simple in-situ growth method to couple Cu-MOF to flower-shaped CuInS 2 And forming a Z-type heterojunction on the surface. With CuInS 2 CuInS compared with Cu-MOF 2 The photocatalytic performance of the Cu-MOF in simulated sunlight is obviously improved. On the one hand, the Z-type electron transfer path not only improves the electron-hole separation efficiency, but also improves the charge transfer efficiency. On the other hand, flower-like CuInS 2 CuInS is improved 2 Cu-MOF surface active site.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and in particular relates to a Z-type heterojunction CuInS 2 Cu-MOF composite material, its preparation method and application, especially in photocatalytic hydrogen evolution.
Background
The hydrogen energy is a high-quality energy source, has the advantages of good heat conductivity, high calorific value, no toxicity and the like, can be stored into various forms, has no secondary pollution to the environment, and meets the requirement of sustainable development. Among the numerous hydrogen production processes, solar-driven photocatalytic decomposition of semiconductor-based materials to produce hydrogen is considered as an important approach to solving energy and environmental problems. The key of the high-efficiency visible light catalytic hydrolysis hydrogen production technology is the selection of photocatalytic materials and the construction of a photocatalytic system. However, the traditional light-driven hydrogen production catalyst has large energy consumption, high cost and complex synthesis process.
The metal sulfide is widely applied to the field of photocatalysis hydrogen evolution. Compared with the traditional catalytic materials of CdS, pbS and TaS 2 Compared with the prior art, the structure of the bimetallic sulfide introduces extra metal atoms, enriches the connection modes among atoms, further leads to structural diversification and endows the material with excellent electric, optical and other properties. However, the photo-generated electron-hole pairs recombine rapidly, limiting CuInS 2 Is a component of the photocatalytic activity of the catalyst.
Metal-organic frameworks (MOFs) have shown different application potential in the fields of photocatalysis, antibacterial, biomedical, battery, electrocatalysis, microextraction, gas adsorption to separations, etc., due to their special properties, including large surface area, adjustable pore structure and topological diversity. Compared with the traditional semiconductor photocatalyst (TiO 2 ,ZnO,WO 3 …) has a higher light capturing efficiency than a light responsive MOF consisting of metal ions and an organic linking agent. In addition, the active sites on the scaffold, intrinsic porosity, tunable pore surface properties, and enlarged surface area not only provide a purposeful structural design, but also enhance electron-hole pairs and support spatial separation of the active species. In particular, cu-MOF materials with variable electronic structures have inexpensive metal ions that can potentially act as photoactive centers, manipulate the potential of CB and the mobility of carriers, and exhibit higher hydrogen-generating activity.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a Z-type heterojunction CuInS 2 Cu-MOF composite material, and its preparation method and application are provided.
The technical scheme adopted by the invention is as follows: z-type heterojunction CuInS 2 The Cu-MOF composite material is prepared by uniformly loading Cu-MOF nano particles in flower-like CuInS 2 CuInS of surface 2 Cu-MOF complexAnd (3) a light combination catalyst.
The Z-type heterojunction CuInS 2 The preparation method of the Cu-MOF composite material specifically comprises the following steps:
(1) 2-amino terephthalic acid (H) 2 ABDC) and copper acetate (Cu) 2 (CH 3 COO) 4 ) Dissolving in Dimethylformamide (DMF), and carrying out ultrasonic treatment and stirring until the solution is completely dissolved to obtain solution A;
optionally, the H 2 ABDC and the Cu 2 (CH 3 COO) 4 The molar ratio of (2) is 1:1-3; preferably 1:2.
(2) CuInS is to 2 Ultrasonically dispersing in the solution A, stirring at room temperature until the solution turns black, and marking as a solution B;
optionally, the CuInS 2 The mass of the catalyst is 50% -80% of the mass of Cu-MOF; preferably 65%.
(3) Pouring the solution B into a reaction kettle, and reacting in an oven at 110+/-10 ℃ for 22-24 hours to obtain a product; centrifugally washing and drying the product to obtain a solid product CuInS 2 Cu-MOF composite.
Optionally, the product is centrifugally washed for several times and dried for several hours to obtain CuInS 2 and/Cu-MOF, wherein the drying temperature is 60-70 ℃ and the drying time is 10-24 hours.
Optionally, the CuInS 2 The method comprises the following steps: cuprous chloride (CuCl) and indium trichloride tetrahydrate (InCl) 3 ·4H 2 O) dissolving in triethanolamine, performing ultrasonic treatment and stirring to form a mixed solution, adding sublimed sulfur, stirring uniformly, transferring into a high-pressure reaction kettle, reacting at 200+ -10deg.C for 48 hr, taking out, centrifuging, and drying to obtain solid product CuInS 2 。
Optionally, the CuCl and the InCl 3 ·4H 2 The molar ratio of O to the sublimed sulfur is 2:1-2; preferably 2:1:1.
Optionally, the CuInS 2 The vacuum drying temperature is 60-70 ℃ and the drying time is 10-24 hours.
The invention further provides a Z-type heterojunction CuInS 2 The Cu-MOF composite material is applied to photocatalytic hydrogen evolution, and is particularly applied to visible light catalytic hydrogen evolution.
Three-dimensional flower-shaped CuInS prepared in specific embodiment of the invention 2 Has larger specific surface area and provides a plurality of active sites for photocatalysis reaction. Meanwhile, the light-absorbing material has a narrower band gap and a wider light-absorbing range, and can meet the requirement of hydrogen production by water splitting. However, when CuInS is used 2 As a photocatalyst, rapid electron-hole recombination still reduces hydrogen production activity. By constructing heterojunction, promoter modification and element doping, the photocatalytic activity can be effectively accelerated. Among other things, the rational design of the heterojunction is very helpful to promote charge separation and photocatalytic activity.
Heterojunction can be classified into type I, type II, and type Z according to electron migration paths. The unique Internal Electric Field (IEF) in the Z-type heterojunction can effectively separate electron hole pairs, reduce the recombination probability, retain strong oxidation-reduction active sites, expand the photoresponse range, improve the photocatalytic activity and the like. CIS and Cu-MOF have appropriate band structures that facilitate the formation of Z-heterostructures, thereby facilitating the separation of photogenerated electron-hole pairs. Flower-like CuInS 2 The uniform and ordered structure provides a good growth environment, exposing more active sites.
The invention adopts a simple in-situ growth method to successfully prepare a new CuInS 2 The Cu-MOF composite material is applied to photocatalysis hydrogen evolution. The Cu-MOF nano particles are uniformly distributed in the flower-shaped CuInS 2 Surface is improved by CuInS 2 Absorption of visible light. In addition, the introduction of Cu-MOF significantly improves flower-like CuInS 2 The separation of the carrier inhibits the recombination of electron holes, thereby improving the photocatalytic activity of the composite material. The result of photocatalysis experiment shows that CuInS 2 Cu-MOF ratio Cu-MOF and CuInS 2 Has higher photocatalytic hydrogen evolution capability. In addition, cuInS was confirmed by experiments and characterization 2 And the presence of a Z-type heterojunction between Cu-MOFs, and suggest a possible photocatalytic reaction mechanism.
Description of the drawings:
FIG. 1 is the presentX prepared in inventive example 1 2 Cu-MOF and CuInS prepared in example 4 2 XRD pattern of CIS/Cu-MOF (a); FT-IR spectra (b) of Cu-MOF and CIS/Cu-MOF prepared in example 4;
FIG. 2 is an SEM image of CIS/Cu-MOF prepared according to example 4 of the present invention (a-d); TEM profile (c-f); EDS image (g);
FIG. 3 is an XPS spectrum of CIS/Cu-MOF prepared in example 4 of the present invention, including the overall spectrum of FIG. 3 (a); FIG. 3 (b) S2 p; fig. 3 (c) In 3d; FIG. 3 (d) O1 s; FIG. 3 (e) Cu 2p;
FIG. 4 is a CuInS prepared in example 4 of the present invention 2 CIS/Cu-MOF and x prepared in example 1 2 A Cu-MOF hydrogen evolution efficiency map (a-b) and a cyclic experiment map (c);
FIG. 5 is a CuInS prepared in example 4 of the present invention 2 CIS/Cu-MOF and x of example 1 2 Fluorescence emission spectrum of Cu-MOF (a); an ultraviolet visible diffuse reflectance spectrum (b); band gap maps (c-d); valence band spectrum (e-f);
FIG. 6 is a CuInS prepared in example 4 of the present invention 2 CIS/Cu-MOF and x prepared in example 1 2 A photo-current response plot (a) of Cu-MOF; EIS impedance (b).
FIG. 7 is a graph of hydrogen evolution efficiency of Cu-MOF prepared in example 1 (a) and CuInS prepared in example 2 2 Hydrogen evolution efficiency profile (b).
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1
Preparation of Cu-MOF materials with different proportions:
(1)H 2 ABDC and Cu 2 (CH 3 COO) 4 Molar ratio 1: cu-MOF preparation of 1: will 0.724g H 2 ABDC and 1.456g Cu 2 (CH 3 COO) 4 Dissolving in 30ml DMF, ultrasonic stirring until completely dissolving, transferring to high pressure reaction kettle, reacting in oven at 110deg.C for 24 hr, and taking out to obtain solid product x 1 Cu-MOF。
(2)H 2 ABDC and Cu 2 (CH 3 COO) 4 Molar ratio 1: cu-MOF preparation of 2: will be 0.362. 0.362g H 2 ABDC and 1.456g Cu 2 (CH 3 COO) 4 Dissolving in 30ml DMF, ultrasonic stirring until completely dissolving, transferring to high pressure reaction kettle, reacting in oven at 110deg.C for 24 hr, and taking out to obtain solid product x 2 Cu-MOF。
(3)H 2 ABDC and Cu 2 (CH 3 COO) 4 Molar ratio 1: cu-MOF preparation of 3: will be 0.181g H 2 ABDC and 1.092g Cu 2 (CH 3 COO) 4 Dissolving in 30ml DMF, ultrasonic stirring until completely dissolving, transferring to high pressure reaction kettle, reacting in oven at 110deg.C for 24 hr, and taking out to obtain solid product x 3 Cu-MOF。
By Na 2 S and Na 2 SO 3 The hydrogen evolution rate of Cu-MOF was investigated by photocatalytic experiments as a hole scavenger. A300W xenon lamp with a 420nm filter was used as a light source for reaction for 5 hours. The hydrogen production is shown in FIG. 7a, from which it can be seen that H 2 ABDC and Cu 2 (CH 3 COO) 4 Molar ratio 1:2, the catalytic activity of the Cu-MOF material is optimal.
Example 2
CuInS of different proportions 2 Is prepared from the following steps:
(1)CuCl、InCl 3 ·4H 2 CuInS having a molar ratio of O to sublimed sulfur of 2:1:1 2 Is prepared from the following steps: 198mg of CuCl and 292mg of InCl 3 ·4H 2 O is dissolved in 60ml of triethanolamine, treated by ultrasonic and stirred to form an aqueous solution, and 256mg of sublimed sulfur S is added 8 After stirring, a solution was formed. The solution was transferred to an autoclave and reacted in an oven at 200 ℃ for 48 hours. Collecting CuInS by centrifugation 2 And washing with ethanol and ionic water several times, drying the product at 60deg.C for 10 hours to give solid product y 1 CIS。
(2)CuCl、InCl 3 ·4H 2 CuInS having a molar ratio of O to sublimed sulfur of 2:2:1 2 Is prepared from the following steps: 198mg of CuCl and 584mg of InCl 3 ·4H 2 O is dissolved in 60ml of triethanolamine, treated by ultrasonic and stirred to form an aqueous solution, and 256mg of sublimed sulfur S is added 8 After stirring, a solution was formed. The solution was transferred to an autoclave and reacted in an oven at 200 ℃ for 48 hours. Collecting CuInS by centrifugation 2 And washing with ethanol and ionized water for several times, and drying the product at 60 deg.C for 10 hr to obtain solid product y 2 CIS。
(3)CuCl、InCl 3 ·4H 2 CuInS with a molar ratio of O to sublimed sulfur of 2:1:2 2 Is prepared from the following steps: 198mg of CuCl and 292mg of InCl 3 ·4H 2 O is dissolved in 60ml of triethanolamine, treated by ultrasonic and stirred to form an aqueous solution, and 512mg of sublimed sulfur S is added 8 After stirring, a solution was formed. The solution was transferred to an autoclave and reacted in an oven at 200 ℃ for 48 hours. Collecting CuInS by centrifugation 2 And washing with ethanol and ionic water several times, drying the product at 60deg.C for 10 hours to give solid product y 3 CIS。
By Na 2 S and Na 2 SO 3 The hydrogen evolution rate of Cu-MOF was investigated by photocatalytic experiments as a hole scavenger. A300W xenon lamp with a 420nm filter was used as a light source for reaction for 5 hours. The hydrogen yield is shown in FIG. 7b, cuCl, inCl 3 ·4H 2 CuInS prepared with a molar ratio of O to sublimed sulfur of 2:1:1 2 Most preferred for experimentation.
Example 3
50-CuInS 2 Preparation of Cu-MOF composite material:
(1)CuInS 2 the preparation method is carried out by a hydrothermal method, and specifically comprises the following steps:
198mg of CuCl and 292mg of InCl 3 ·4H 2 O is dissolved in 60ml of triethanolamine, treated by ultrasonic and stirred to form an aqueous solution, and 256mg of sublimed sulfur S is added 8 After stirring, a solution was formed. The solution was transferred to an autoclave and reacted in an oven at 200 ℃ for 48 hours. Collecting CuInS by centrifugation 2 And water was used several times with ethanol and ionic water, and the product was dried at 60 ℃ for 10 hours.
(2) Will be 0.362. 0.362g H 2 ABDC (2 mmol) and 1.456g Cu 2 (CH 3 COO) 4 (4 mmol) dissolved in 30ml DMF, sonicated and stirred until completely dissolved; 0.85g CuInS was added 2 Ultrasonic dissolving and stirring at room temperature until the solution turns black, and marking as a mixed solution; the mixed solution was poured into a reaction kettle and reacted in an oven at 110℃for 24 hours. Centrifugally washing with ethanol and ionized water for several times, and drying for several hours to obtain a solid product of 50-CuInS 2 The Cu-MOF composite was designated 50-CIS/Cu-MOF.
Example 4
65-CuInS 2 Preparation of Cu-MOF composite material:
(1)CuInS 2 is prepared as in example 3;
(2) Will be 0.362. 0.362g H 2 ABDC and 1.456g Cu 2 (CH 3 COO) 4 Dissolving in 30ml DMF, ultrasound and stirring until completely dissolved; 1.58g of CuInS was added 2 Ultrasonic dissolving and stirring at room temperature until the solution turns black, and marking as a mixed solution; the mixed solution was poured into a reaction kettle and reacted in an oven at 110℃for 24 hours. Centrifugally washing with ethanol and ionized water for several times, and drying for several hours to obtain a solid product of 65-CuInS 2 The Cu-MOF composite was designated 65-CIS/Cu-MOF.
Example 5
80-CuInS 2 Preparation of Cu-MOF composite material:
(1)CuInS 2 is prepared as in example 3;
(2) Will be 0.362. 0.362g H 2 ABDC and 1.456g Cu 2 (CH 3 COO) 4 Dissolving in 30ml DMF, ultrasound and stirring until completely dissolved; 3.4g of CuInS was added 2 Ultrasonic dissolving and stirring at room temperature until the solution turns black, and marking as a mixed solution; the mixed solution was poured into a reaction kettle and reacted in an oven at 110℃for 24 hours. Centrifugally washing with ethanol and ionized water for several times, and drying for several hours to obtain a solid product of 80-CuInS 2 The Cu-MOF composite was designated 80-CIS/Cu-MOF.
Further, how the embodiments of the present invention may be carried out to achieve the objects of the present invention will be described with reference to the accompanying drawings, in which:
referring to FIG. 1, the crystalline phases of CIS, cu-MOF and CIS/Cu-MOF of the present invention were determined using X-ray diffraction spectroscopy (XRD). As shown in FIG. 1 (a), the prepared Cu-MOF diffraction peaks are respectively located at 10.3 degrees, 11.85 degrees, 13.39 degrees, 16.83 degrees, 18.09 degrees, 20.82 degrees and 24.82 degrees, and are well matched with Cu-MOF in the literature. Four distinct diffraction peaks of CIS at 27.88 °, 32.3 °, 46.35 °, and 54.86 ° correspond to the (112), (220), (204), and (116) planes of CIS (PDF # 27-0159), respectively. Most notably, both Cu-MOF and CIS exhibited characteristic peaks in the CIS/Cu-MOF samples, indicating successful preparation of the material.
Please refer to fig. 1 (b), which shows the chemical bond and functional group of the sample studied using Fourier Transform Infrared (FTIR) spectroscopy. Cu-MOF at 759cm -1 The peak at the point is caused by Cu-O stretching vibration, and the bifurcation peak is at 3247 cm and 3423cm -1 Is NH of 2-amino terephthalic acid linker 2 The group is obtained. Located at 1338, 1465 and 1547cm -1 The absorption peaks of (a) were respectively given a c—n bond, a c=o bond and a c=n bond stretching vibration, demonstrating the condensation reaction. These characteristic peaks belonging to Cu-MOF remain in the spectrum of the CIS/Cu-MOF sample, further demonstrating the presence of Cu-MOF in the CIS/Cu-MOF sample.
Referring to FIGS. 2 (a-d), the morphology of CIS, cu-MOF and CIS/Cu-MOF was studied using a Scanning Electron Microscope (SEM). As shown in FIG. 2 (a), the prepared Cu-MOF showed irregular nanoparticles with a diameter of about 20 nm. FIG. 2 (b) shows the prepared CuInS 2 Has clear flower-like structure and particle size of 2-3 μm. In FIG. 2 (c), the CIS surface is visible as a flower at 500nm, with a large surface area. In fig. 2 (d), cu-MOF nanoparticles are coupled to the flower-like CIS surface. The microstructure of the catalyst was further studied using a High Resolution Transmission Electron Microscope (HRTEM). As shown in FIG. 2 (e-f), a lattice having a spacing of 0.32nm was clearly observed, belonging to CIS (112). Furthermore, EDS map of CIS/Cu-MOF FIG. 2 (g) shows that this composite contains C, N, O, S, in and Cu elements.
Referring to fig. 3, the elemental and surface electron states of the samples were studied using X-ray photoelectron spectroscopy (XPS). As shown in fig. 3 (a), investigation of XPS spectra revealed that characteristic peaks of CIS and Cu-MOF exist at the CIS/Cu-MOF surface at the same time, including C, N, O, S, in and Cu. Two peaks in the figure. The two characteristic peaks at 160.5 and 162.9eV in FIG. 3 (b) are attributed to Cu 2p1/2 and Cu 2p3/2. The signals at 451.4 and 443.9eV In FIG. 3 (c) demonstrate the presence of In 3d3/2 and In 3d 5/2. In fig. 3 (d), two O1s peaks at 531.8 and 533.1eV are attributed to the C-O and c=o groups. In FIG. 3 (e), at 934.6 and 950eV, cu is attributed to Cu 2p3/2 and Cu 2p1/2 however, after CIS introduction + The amount of (C) is significantly increased, which means that the CIS becomes Cu 2+ Electron donors of (c) are included. Furthermore, for CIS/Cu-MOF, the Cu 2p peak shifts to higher binding energy than for Cu-MOF, which represents electron migration due to the difference in work function, the internal electric fields are tightly bound together, again demonstrating that CIS/Cu-MOF forms a tight heterojunction.
Photocatalytic hydrogen evolution
By Na 2 S and Na 2 SO 3 The hydrogen evolution rate of the samples was studied by photocatalytic experiments as hole scavengers. A300W xenon lamp with a 420nm filter was used as a light source for reaction for 5 hours. Prior to the experiment, it was determined that H was not obtained in the absence of catalyst, light or water 2 . H of the sample in FIG. 4a 2 The evolution amount steadily increased within 5h. H of sample 2 Evolution Rate, see FIG. 4 (a-b), CIS (150.06. Mu. Mol. G -1 ·h -1 ) And Cu-MOF (101.92. Mu. Mol. G) -1 ·h -1 ) Is poor, probably due to the rapid recombination of photogenerated electron-hole pairs. Notably, the composite CIS/Cu-MOF exhibits excellent hydrogen evolution performance compared to CIS and Cu-MOF, which should be due to the construction of the Z-heterojunction facilitating space charge separation. Wherein, H of 65-CIS/Cu-MOF 2 Evolution rate reaches 1002.35 mu mol g -1 ·h -1 6.7 times that of CIS and 9.8 times that of Cu-MOF, respectively.
After 5 cycle experiments, please refer to fig. 4 (c), the photocatalytic hydrogen evolution activity of CIS/Cu-MOF was still stable.
Referring to fig. 5 (a), photoluminescence (PL) spectral characterization was performed to gain a more thorough understanding of charge transfer. The higher fluorescence emission peak means higher recombination rate of electron-hole pairs. PL emission intensities of CIS and Cu-MOF indicate rapid recombination of photogenerated electron-hole pairs, which is detrimental to photocatalytic H 2 Is precipitated.However, the PL emission intensity of CIS/Cu-MOF is significantly lower than CIS and Cu-MOF, indicating that the construction of the heterojunction eases the recombination of photogenerated carriers.
Please refer to fig. 5 (b) for measuring the light capturing capability of the sample by ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). The CIS/Cu-MOF has stronger visible light absorption capacity compared with the CIS/Cu-MOF, and the light absorption edge is close to 570nm. Further, as shown in FIG. 5 (c-d), band gaps (Eg) of CIS and Cu-MOF were obtained by the Kubelka-Munk function to be 1.85 and 2.8eV. From XPS valence band spectrum as shown in FIG. 5 (e-f), the valence band maxima (EVB) of CIS and Cu-MOF were-0.6 and 0.9eV, respectively. The maximum conduction bands (ECB) for CIS and Cu-MOF were-2.45 and-1.9 eV (ecb=evb-Eg), respectively.
To study interfacial charge separation, photoelectrochemical (PEC) measurements were performed. The transient photocurrent response was detected and the photopotential of the 300WXe lamp at the 420nm filter was studied. Referring to fig. 6 (a), the photocurrent density of CIS/Cu-MOF in the sample is highest because the interfacial interaction between CIS and Cu-MOF is improved due to uniform dispersion of the structure. Referring to Electrochemical Impedance Spectroscopy (EIS) analysis in fig. 6 (b), it is shown that the nyquist arc radius of CIS/Cu-MOF in the sample is significantly minimal, which is due to the excellent conductivity of flower-like CIS, which increases the interfacial charge transfer rate.
The foregoing is only a preferred or exemplary embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications or adaptations can be made without departing from the principles of the present invention, and such modifications or adaptations are intended to be within the scope of the invention.
Claims (8)
1. Z-type heterojunction CuInS 2 Cu-MOF composite material characterized in that the Z-type heterojunction CuInS 2 Cu-MOF nano particles in Cu-MOF composite material are uniformly loaded on flower-shaped CuInS 2 A surface; the CuInS 2 The mass of the (C) is 50-80% of the mass of the Cu-MOF.
2. A Z-heterojunction CuInS as claimed in claim 1 2 The preparation method of the Cu-MOF composite material is characterized by comprising the following steps ofThe steps are as follows:
(1) Dissolving 2-amino terephthalic acid and copper acetate in dimethylformamide, and carrying out ultrasonic treatment and stirring until the 2-amino terephthalic acid and the copper acetate are completely dissolved to obtain a solution A;
(2) CuInS is to 2 Ultrasonically dispersing in the solution A, stirring at room temperature until the solution turns black, and marking as a solution B;
(3) Pouring the solution B into a reaction kettle, and reacting in an oven at 100-120 ℃ for 22-24 hours to obtain a product; centrifuging, washing and drying the product to obtain CuInS 2 Cu-MOF composite.
3. The Z-heterojunction CuInS of claim 2 2 The preparation method of the Cu-MOF composite material is characterized in that the molar ratio of the 2-amino terephthalic acid to the copper acetate is 1:1-3.
4. The Z-heterojunction CuInS of claim 2 2 A method for preparing a Cu-MOF composite material is characterized in that the CuInS 2 The method comprises the following steps: dissolving cuprous chloride and indium trichloride tetrahydrate in triethanolamine, performing ultrasonic treatment, stirring to form a mixed solution, adding sublimed sulfur, stirring uniformly, transferring into a high-pressure reaction kettle, reacting at 190-210 ℃ for 36-48 hours, taking out, centrifuging, and drying to obtain a solid product CuInS 2 。
5. The Z-heterojunction CuInS of claim 4 2 The preparation method of the Cu-MOF composite material is characterized in that the molar ratio of cuprous chloride, indium trichloride tetrahydrate and sublimed sulfur is 2:1-2.
6. The Z-heterojunction CuInS of claim 4 2 The preparation method of the Cu-MOF composite material is characterized in that the drying is vacuum drying, the drying temperature is 60-70 ℃, and the drying time is 10-24 hours.
7. The Z-heterojunction CuInS of claim 2 2 Cu-MOF composite materialThe preparation method of (2) is characterized by CuInS 2 The mass of the catalyst is 50 to 80 percent of the mass of the in-situ synthesized Cu-MOF.
8. A Z-heterojunction CuInS as claimed in claim 1 2 The use of a Cu-MOF composite material, characterized in that the Z-type heterojunction CuInS 2 The Cu-MOF composite material is used for photocatalytic hydrogen evolution.
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