CN111468143A - Cuprous oxide/molybdenum disulfide composite material and preparation method and application thereof - Google Patents
Cuprous oxide/molybdenum disulfide composite material and preparation method and application thereof Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 95
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229940112669 cuprous oxide Drugs 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 90
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000004065 semiconductor Substances 0.000 claims abstract description 25
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 12
- 229940012189 methyl orange Drugs 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229960005070 ascorbic acid Drugs 0.000 claims description 14
- 235000010323 ascorbic acid Nutrition 0.000 claims description 14
- 239000011668 ascorbic acid Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000001782 photodegradation Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Hydrology & Water Resources (AREA)
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Abstract
The invention discloses a Cu2O/1T MoS2A composite material and a preparation method and application thereof belong to the technical field of optical material preparation, and the composite material is MoS2(1T MoS2) Cu with p-type semiconductor property grown in situ by taking nanosheet as substrate2O material (Cu)2O/1T MoS2) And is applied to the photodegradation of methyl orange. The composite material is prepared by obtaining metal phase MoS2Metal phase MoS2Has very good conductivity and is beneficial to semiconductor material Cu2The fast transfer of the electron-hole pair generated by O, thereby reducing the recombination of the electron-hole pair and greatly improving the Cu content2Optical properties of O. And is successfully applied to the photodegradation of methyl orange, thereby greatly improving Cu2Photodegradability of the O pair.
Description
Technical Field
The invention belongs to the technical field of optical material preparation, and particularly relates to Cu2O/1T MoS2A composite material and a preparation method and application thereof.
Background
Cu2O is an abundant and low-cost metal oxide semiconductor and has the properties of photochemistry, photoelectrochemistry, electrochemistry and the like. However, in the field of photocatalysis, electron-hole pairs generated under illumination can recombine in a short time, so that the photocatalysis performance of the electron-hole pairs is reduced, and the problem of Cu is solved2The problem of electron hole pair recombination in the O material is very important to improve its photocatalytic performance. And MoS2As a typical transition metal sulfide, the graphene-like carbon nano-composite material has a special graphene-like structure and unique physicochemical properties, particularly a metal phase MoS2Has a plurality of active sites and excellent conductivity, and is a very promising material.
Disclosure of Invention
The invention aims to provide Cu aiming at the defects of the prior art2O/1T MoS2A composite material and a preparation method and application thereof. The composite material utilizes metal phase MoS2To compensate for the advantages of the semiconductor material Cu2Deficiency of O to promote Cu2The photocatalytic performance of O is applied to the photodegradation of methyl orange.
The purpose of the invention is realized by the following technical scheme: cu2O/1T MoS2Composite material of said Cu2O/1T MoS2Composite material with metal phase MoS2In-situ growth of Cu for a substrate2O, the Cu2O/1T MoS2The composite material is prepared by the following method:
(1) weighing ammonium molybdate and thiourea according to the molar ratio of 1:7-14, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at the temperature of 180-220 ℃ for 14-22h, cooling to room temperature, centrifugally separating at the rotating speed of 8500r/min for 10min, collecting precipitates, washing the precipitates with water and ethanol for 2 times respectively, and drying in vacuum at the temperature of 60 ℃ until the liquid is completely evaporated to obtain the semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into a saturated copper salt solution to control the semiconductor phase MoS2The concentration of the nano-sheets is 0.57-2.28 mmol/L, ultrasonic treatment is carried out for more than 6h, then centrifugal separation is carried out for 10min at the rotating speed of 8500r/min, precipitates are collected, water and ethanol are respectively used for washing the precipitates for 2 times, and vacuum drying is carried out at the temperature of 60 ℃ until liquid is completely evaporated, thus obtaining the metal phase MoS2Nano-sheet。
(4) The obtained metal phase MoS2Dispersing the nano-sheets into deionized water to maintain metal phase MoS2The concentration of the nano-sheets is 6.25-25 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2The concentration of O is 12.5-50 mmol/L, stirring and mixing evenly, then adding ascorbic acid to make the concentration of ascorbic acid be 0.05-0.2 mol/L, stirring and mixing evenly to form homogeneous aqueous solution.
(5) Adjusting pH of the homogeneous aqueous solution to 9-12 with NaOH solution, heating at 60 deg.C and stirring for 5-12min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/1T MoS2。
Further, the copper salt is a divalent copper salt such as copper chloride, copper nitrate, copper sulfate, and the like.
The invention also provides Cu2O/1T MoS2Application of the composite material in degrading methyl orange.
Compared with the prior art, the invention has the beneficial effects that: firstly proposes the synthesis of metal phase MoS in the common cupric salt by a long-time high-power ultrasonic method2Nanosheet and Cu prepared by using nanosheet as substrate2O/1T MoS2Composite material using metal phase MoS2Numerous active sites and advantages of good conductivity, in the form of a metal phase MoS2Modification of Cu as a substrate2O nanoparticles, the active sites present in large numbers contributing to Cu2Surface nucleation of O nanoparticles to allow uniform growth of a large number of nanoparticles on MoS2Surface, simultaneous metal phase MoS2The excellent conductivity is beneficial to the rapid transfer of electron-hole pairs generated under illumination, and the recombination of the electron-hole pairs is reduced, so that the Cu content is improved2The photocatalytic performance of O, and is successfully applied to the photodegradation of methyl orange.
Drawings
FIG. 1 shows the metal phase MoS prepared in example 12Scanning Electron Microscopy (SEM);
FIG. 2 shows the metal phase MoS prepared in example 12High Resolution Transmission Electron Microscopy (HRTEM);
FIG. 3 is a semiconductor phase MoS prepared in example 12Nanosheet (2H MoS)2) And metal phase MoS2Nanosheet (1 TMoS)2) A raman map of;
FIG. 4 shows Cu prepared in example 12O/1T MoS2X-ray diffraction pattern (XRD);
FIG. 5 shows Cu prepared in example 12O/1T MoS2Scanning Electron Microscopy (SEM);
FIG. 6 shows Cu prepared in example 12O/1T MoS2Transmission Electron Microscopy (TEM);
FIG. 7 is a Raman plot of the materials prepared in example 1 and comparative examples 1-2;
FIG. 8 is a UV absorption spectrum of the product obtained in example 1.
Detailed Description
Example 1
The invention provides a Cu2O/1T MoS2The composite material is prepared by the following steps:
(1) weighing ammonium molybdate and thiourea according to a molar ratio of 1:14, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at 220 ℃ for 18h, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, washing the precipitate with water and ethanol for 2 times, and vacuum drying at 60 ℃ until the liquid is completely evaporated to obtain semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into a saturated copper chloride solution to control the semiconductor phase MoS2The concentration of the nano-sheets is 1.14 mmol/L, ultrasonic treatment is carried out for 8h, then centrifugal separation is carried out for 10min at the rotating speed of 8500r/min, precipitates are collected, water and ethanol are respectively used for washing the precipitates for 2 times, and then vacuum drying is carried out at the temperature of 60 ℃ until liquid is completely evaporated, thus obtaining the metal phase MoS2Nanosheets. FIG. 1 shows the prepared metal phase MoS2A Scanning Electron Micrograph (SEM) of (A) and a high-resolution transmission electron micrograph (HRTEM) of (B) in FIG. 2. from FIGS. 1 to 2, it can be seen that the metal phase MoS is present2The nano-sheets are uniformly dispersed, the diameter is about 150-300nm, and the distance between the sheets is about 0.6 nm. The good dispersibility and the lamellar structure with the nano-scale size greatly increase the specific surface area of the material, thereby improving the catalytic performance of the catalyst. FIG. 3 is a Raman plot of the semiconductor phase prepared in example 1, wherein the MoS of the semiconductor phase2Nanosheets are at 378 and 404cm-1Has two peaks corresponding to in-plane E1 2gWith dough A1gA belt; and 1TMoS2Shows a typical metal phase MoS2In a vibration mode of 140cm-1Attributable to the metal phase MoS2Elastic vibration mode between Mo and Mo of 190,275 and 331cm-1Is phonon vibration mode, 370cm-1Ascribed to MoS2In-plane vibration mode of (1).
(4) The obtained metal phase MoS2Dispersing the nano-sheets into deionized water to maintain metal phase MoS2The concentration of the nano-sheets is 12.5 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2The concentration of O is 25.0 mmol/L, the mixture is stirred and mixed evenly, ascorbic acid is added to ensure that the concentration of the ascorbic acid is 0.1 mol/L, and the mixture is stirred and mixed evenly to form homogeneous aqueous solution.
(5) Adjusting pH of the homogeneous aqueous solution to 12 with NaOH solution, heating at 60 deg.C and stirring for 10min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, and vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/1T MoS2. FIG. 4 shows Cu being prepared2O/1T MoS2In which the peaks at the 14.6, 39.8, 49.9 positions are MoS2And peaks at the 36.1, 42.7, 61 and 74.1 positions are Cu2Characteristic peak of O. FIG. 5 shows Cu prepared in example 12O/1T MoS2Scanning Electron Micrograph (SEM) of (1) and FIG. 6 shows Cu prepared in example 12O/1T MoS2A Transmission Electron Micrograph (TEM) of the specimen,from these two figures, it can be seen that a large amount of Cu with a diameter of about 20nm is present2The O nano particles are uniformly grown in the metal phase MoS2This results in Cu2O nanoparticles and 1T MoS2The material is in full contact with the other material, so that the transfer of photoproduction electrons is facilitated, the separation efficiency of electron hole pairs is improved, and the photocatalysis capability of the material is improved.
20mg of Cu prepared in example 12O/1T MoS2Putting the mixture into a photodegradation reaction tank, adding the mixture into a 50m L10 mg/L methyl orange solution, carrying out ultrasonic treatment for 0.5h to obtain a suspension, taking 4m L of the suspension, carrying out centrifugal separation for 10min at the rotating speed of 6000r/min to obtain a supernatant, marking as sample 1, connecting the reaction tank with circulating water, controlling the temperature to be 25 ℃, continuously stirring the mixture for 0.5h in the dark to achieve an adsorption equilibrium state, taking 4m L of the suspension, carrying out centrifugal separation for 10min at the rotating speed of 6000r/min to obtain a supernatant, marking as sample 2, switching on a light source, continuously stirring at room temperature, extracting 4m L of the suspension at selected time intervals, respectively marking as sample 3, sample 4 and the like, carrying out centrifugal separation for 10min at the rotating speed of 6000r/min to obtain the supernatant, and finally carrying out ultraviolet test on the supernatant to obtain the photodegradation efficiency, wherein an ultraviolet absorption spectrogram 8 is observed that the content of the methyl orange in the solution is gradually reduced along with the increase of the reaction time-Is captured by dissolved oxygen to generate O2 -，·O2 -And a cavity h+The organic acid has strong oxidizability and is subjected to oxidation-reduction reaction with methyl orange, so that the effect of degrading the methyl orange is achieved, and the degradation efficiency reaches 90%.
Comparative example 1: preparation of Cu2O/2H MoS2Composite material
(1) Weighing ammonium molybdate and thiourea according to a molar ratio of 1:14, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at 220 deg.C for 18h, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, washing the precipitate with water and ethanol respectivelyWashing for 2 times, and vacuum drying at 60 deg.C until the liquid is completely evaporated to obtain semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into deionized water to maintain the semiconductor phase MoS2The concentration of the nano-sheets is 12.5 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2The concentration of O is 25.0 mmol/L, the mixture is stirred and mixed evenly, ascorbic acid is added to ensure that the concentration of the ascorbic acid is 0.1 mol/L, and the mixture is stirred and mixed evenly to form homogeneous aqueous solution.
(4) Adjusting pH of the homogeneous aqueous solution to 12 with NaOH solution, heating at 60 deg.C and stirring for 10min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, and vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/2H MoS2。
Cu obtained in comparative example 12O/2H MoS2Methyl orange was degraded by the method of example 1, with a degradation efficiency of 30% due to 2H MoS2Poor electron transport may inhibit the separation of electron-hole pairs to some extent, resulting in poor methyl orange degradation efficiency.
Comparative example 2: preparation of Cu2O nanoparticles
(1) Mixing CuSO4·5H2Adding O into deionized water to make CuSO4·5H2The concentration of O is 25.0 mmol/L, the mixture is stirred and mixed evenly, ascorbic acid is added to ensure that the concentration of the ascorbic acid is 0.1 mol/L, and the mixture is stirred and mixed evenly to form homogeneous aqueous solution.
(2) Adjusting pH of the homogeneous aqueous solution to 12 with NaOH solution, heating at 60 deg.C and stirring for 10min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, and vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2And (3) O nanoparticles.
Cu obtained in comparative example 22The method of example 1 is adopted to degrade methyl orange by O nano particles, and the degradation efficiency of the methyl orange is 61 percent and is obviously lower than that of Cu2O/1T MoS2Degradation efficiency of 90%.
FIG. 7 is a Raman map of the materials prepared in example 1 and comparative examples 1-2, from which Cu can be observed2Raman peak positions of O at 148 and 174cm-1。Cu2O/1T MoS2In the presence of Cu2Raman characteristic peaks of O (148 cm and 174 cm)-1Also, 1TMoS exists2Characteristic peaks of 140, 190, 275331 and 370cm-1。Cu2O/2H MoS2In the presence of Cu2Raman characteristic peaks of O (148 cm and 174 cm)-1Also, 2H MoS is present2Characteristic peaks 378 and 404cm-1. Thereby proving MoS2The metal phase of (a) is not destroyed during the synthesis.
Example 2
The invention provides a Cu2O/1T MoS2The composite material is prepared by the following steps:
(1) weighing ammonium molybdate and thiourea according to a molar ratio of 1:7, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at 180 ℃ for 22h, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, washing the precipitate with water and ethanol for 2 times, and vacuum drying at 60 ℃ until the liquid is completely evaporated to obtain semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into a saturated copper nitrate solution to control the semiconductor phase MoS2Ultrasonic treating for 6h at concentration of 0.57 mmol/L, centrifuging at 8500r/min for 10min, collecting precipitate, washing with water and ethanol for 2 times, and vacuum drying at 60 deg.C until the liquid is completely evaporated to obtain metal phase MoS2Nanosheets.
(4) The obtained metal phase MoS2Dispersing the nano-sheets into deionized water to maintain metal phase MoS2The concentration of the nano-sheets is 6.25 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2O concentration of 12.5 mmol/L, stirring and mixing evenly, then adding ascorbic acid to ensure that the concentration of the ascorbic acid is 0.05 mol/L, stirring and mixing evenly to form a homogeneous aqueous solution.
(5) Adjusting pH of the homogeneous aqueous solution to 9 with NaOH solution, heating at 60 deg.C and stirring for 5min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, and vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/1T MoS2。
Cu obtained in example 22O/1T MoS2The composite material is degraded by the method in the embodiment 1, and the degradation efficiency reaches 90%.
Example 3
The invention provides a Cu2O/1T MoS2The composite material is prepared by the following steps:
(1) weighing ammonium molybdate and thiourea according to the molar ratio of 1:14, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at 220 ℃ for 14h, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, washing the precipitate with water and ethanol for 2 times, and vacuum drying at 60 ℃ until the liquid is completely evaporated to obtain semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into a saturated copper sulfate solution to control the semiconductor phase MoS2The concentration of the nano-sheets is 2.28 mmol/L, ultrasonic treatment is carried out for 10h, then centrifugal separation is carried out for 10min at the rotating speed of 8500r/min, precipitates are collected, water and ethanol are respectively used for washing the precipitates for 2 times, and then vacuum drying is carried out at the temperature of 60 ℃ until liquid is completely evaporated, thus obtaining the metal phase MoS2Nanosheets.
(4) The obtained metal phase MoS2Dispersing the nano-sheets into deionized water to maintain metal phase MoS2The concentration of the nano-sheets is 6.25-25 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2The concentration of O is 50 mmol/L, stirringStirring and mixing evenly, then adding ascorbic acid to ensure that the concentration of the ascorbic acid is 0.2 mol/L, stirring and mixing evenly to form a homogeneous aqueous solution.
(5) Adjusting pH of the homogeneous aqueous solution to 12 with NaOH solution, heating at 60 deg.C and stirring for 12min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, and vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/1T MoS2。
Cu obtained in example 32O/1T MoS2The composite material is degraded by the method in the embodiment 1, and the degradation efficiency reaches 90%.
Claims (3)
1. The cuprous oxide/molybdenum disulfide composite material is characterized in that the Cu2O/1T MoS2Composite material with metal phase MoS2In-situ growth of Cu for a substrate2O, the Cu2O/1T MoS2The composite material is prepared by the following method:
(1) weighing ammonium molybdate and thiourea according to the molar ratio of 1:7-14, dissolving in water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the ammonium molybdate in the water is 1 mmol/L.
(2) Transferring the mixed solution into a stainless steel reaction kettle, reacting at the temperature of 180-220 ℃ for 14-22h, cooling to room temperature, centrifugally separating at the rotating speed of 8500r/min for 10min, collecting precipitates, washing the precipitates with water and ethanol for 2 times respectively, and drying in vacuum at the temperature of 60 ℃ until the liquid is completely evaporated to obtain the semiconductor phase MoS2Nanosheets.
(3) The obtained semiconductor phase MoS2Dispersing the nano-sheets into a saturated copper salt solution to control the semiconductor phase MoS2The concentration of the nano-sheets is 0.57-2.28 mmol/L, ultrasonic treatment is carried out for more than 6h, then centrifugal separation is carried out for 10min at the rotating speed of 8500r/min, precipitates are collected, water and ethanol are respectively used for washing the precipitates for 2 times, and vacuum drying is carried out at the temperature of 60 ℃ until liquid is completely evaporated, thus obtaining the metal phase MoS2Nanosheets.
(4) The obtained metal phase MoS2Dispersing the nano-sheets into deionized water to maintain metal phase MoS2The concentration of the nano-sheets is 6.25-25 mmol/L, and CuSO is added4·5H2O solution, so that CuSO4·5H2The concentration of O is 12.5-50 mmol/L, stirring and mixing evenly, then adding ascorbic acid to make the concentration of ascorbic acid be 0.05-0.2 mol/L, stirring and mixing evenly to form homogeneous aqueous solution.
(5) Adjusting pH of the homogeneous aqueous solution to 9-12 with NaOH solution, heating at 60 deg.C and stirring for 5-12min, cooling to room temperature, centrifuging at 8500r/min for 10min, collecting precipitate, vacuum drying at 60 deg.C until the liquid completely disappears to obtain Cu2O/1T MoS2。
2. The cuprous oxide/molybdenum disulfide composite of claim 1, wherein the copper salt is a divalent copper salt such as cupric chloride, cupric nitrate, cupric sulfate, etc.
3. Use of cuprous oxide/molybdenum disulfide composite according to claim 1 for degrading methyl orange.
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