CN112121826A - 1T @2H-MoS2/SnS2Preparation method, product and application of visible light response photocatalyst - Google Patents
1T @2H-MoS2/SnS2Preparation method, product and application of visible light response photocatalyst Download PDFInfo
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- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 58
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 230000004298 light response Effects 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 75
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 239000011684 sodium molybdate Substances 0.000 claims description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 16
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 4
- KKHJTSPUUIRIOP-UHFFFAOYSA-J tetrachlorostannane;hydrate Chemical compound O.Cl[Sn](Cl)(Cl)Cl KKHJTSPUUIRIOP-UHFFFAOYSA-J 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- 239000002131 composite material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J35/39—
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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
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
-
- 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
Abstract
The invention discloses a 1T @2H-MoS2/SnS2The invention discloses a preparation method of a photocatalyst, relating to the technical field of photocatalysts and comprising the following steps: (1) mixing and preparing the liquid; (2) carrying out hydro-thermal synthesis; (3) separating and washing to obtain 1T @2H-MoS2/SnS2A photocatalyst. The invention also provides 1T @2H-MoS prepared by the preparation method2/SnS2A photocatalyst and an application thereof. The invention has the beneficial effects that: the invention adopts a one-step synthesis method to prepare the product, the preparation method is simple, and the prepared 1T @2H-MoS2/SnS2The heterogeneous compound has good photocatalytic degradation performance, and has good stability and recyclability.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to 1T @2H-MoS2/SnS2A preparation method, a product and application of a visible light response photocatalyst.
Background
The design of the composite photocatalyst with simple preparation process, controllable components and high visible light catalytic activity is semiconductor catalysisThe field of agents is a very important research direction. MoS, two important metal sulfide semiconductor materials2And SnS2All fall within the visible range (around 2 eV), and have certain structural similarity, so that MoS is constructed2/SnS2The heterojunction is valuable for developing corresponding photocatalysis research.
Although there are several instances regarding MoS2/SnS2Report of heterojunction catalytic Performance (Zhang J, Huang G, Zeng J, et al2 nanosheets coupled with 2D ultrathin MoS2 nanolayers as face-to-face 2D/2D heterojunction photocatalysts with excellent photocatalytic and photoelectrochemical activities[J].Journal of Alloys and Compounds,2018,726-735，Xiao X,Wang Y,Xu X,et al.Preparation of the flower-like MoS2/SnS2 heterojunction as an efficient electrocatalyst for hydrogen evolution reaction[J]Molecular Catalysis,2020,487: 110890), but is essentially limited in composition to a single 2H phase MoS2. The 2H phase is not very conductive and has few active sites, so the catalytic performance is not ideal.
In fact, MoS2Can exist in a stable mixed phase of a semiconducting phase (2H) and a metastable metallic phase (1T) or even 1T-2H, 1T-MoS2Has the greatest advantage of good conductivity, and the conductivity is 2H-MoS 210 of semiconductor phase7More than two times, the other advantage is that more marginal active sites are exposed. It is well known that for semiconductor pn junction photocatalysts, the driving force for carrier separation at the interface is a built-in electric field, and carrier separation and migration at the interface is not ideal due to the poor conductivity of the semiconductor itself. Therefore, many heterojunction photocatalysts add noble metals or acetylene black nanodots having good conductivity as bridges, in particular. Construction of SnS consisting of flakes2And 1T @2H-MoS2The composite structure composed of the mixed phases has practical value, and the photocatalytic performance of the system is improved by utilizing the synergistic effect of the two phases. In such a mixed system, 2H-MoS2And SnS2Combine to form a semiconductor heterojunction, act as a good photosensitizer and catalyst, and 1T-MoS2Main chargerChannels and co-catalysts for electron transport.
In the existing literature reports, MoS2/SnS2The preparation of nanocomposites usually employs more than two steps, i.e. the separate synthesis of MoS in advance2And SnS2And then recombining the one or two nanostructures. The existing one-step synthesis method is to directly mix various raw materials in a reaction kettle, and the one-pot method greatly simplifies the preparation process and is beneficial to industrial production. The patent with the publication number of CN104821240A discloses a one-step hydrothermal synthesis method of SnS2/MoS2The basic process is that tin tetrachloride and L-cysteine are firstly dissolved in water, then sodium molybdate solution is added to generate tin molybdate precipitate, and the mixed product is reacted for 24 hours under the hydrothermal condition of 220-240 ℃ to obtain the target product. The main application of the method is to be applied to electrode materials rather than the field of photocatalysis, and the important factor for limiting the application of the photocatalysis field is MoS in a synthetic product2Present as a stable 2H phase.
Disclosure of Invention
The invention aims to solve the technical problem of providing 1T @ 2H-MoS which has simple preparation method and is suitable for photocatalyst2/SnS2The preparation method of (1).
The invention solves the technical problems through the following technical means:
1T @2H-MoS2/SnS2The preparation method of the visible light response photocatalyst comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.151-0.605 part of hydrated sodium molybdate and 0.191-0.763 part of hydrated tin chloride in deionized water, then adding citric acid and 1.035-1.439 parts of thiourea, stirring and dissolving, and then, the pH value of the solution is 3-5;
(2) hydrothermal synthesis: heating the solution in the step (1) to 220 ℃, preserving heat for 24 hours, and cooling to room temperature;
(3) separation and washing: centrifuging the reaction product in the step (2), washing and drying to obtain 1T @2H-MoS2/SnS2A photocatalyst.
Has the advantages that: the invention adopts a one-step synthesis method to prepare the productThe preparation method is simple, the invention firstly mixes the hydrated sodium molybdate and the hydrated tin chloride, then adds the thiourea, controls the mol ratio of the Mo and the Sn, changes the composite proportion of the two compounds and the MoS2The proportion of the two phases in the mixed phase is such that 1T-MoS2、2H-MoS2And SnS2A synergistic effect is generated.
1T @2H-MoS prepared by adopting preparation method disclosed by the invention2/SnS2The heterogeneous composite has 1T-MoS2And 2H-MoS2Two lattices, small size spherical MoS2SnS attached to large scale2On the nano-sheet. The prepared 1T @2H-MoS2/SnS2The heterogeneous compound has good photocatalytic degradation performance, and has good stability and recyclability.
The addition of citric acid is intended to maintain an acidic solution environment, so that Mo and Sn can be effectively prevented from being oxidized, and the addition amount of citric acid needs to be strictly controlled to control the PH of the solution to be between 3 and 5. If citric acid is not present, the final synthesis product of the Sn source is SnO2Instead of SnS2Even further contains a certain amount of MoO3。
Preferably, the weight fraction of the added citric acid is 0.827-2.174 parts, and the added deionized water is 80 mL.
Preferably, in the step (1), the weight part of the hydrated sodium molybdate is 0.151 part, the weight part of the hydrated tin chloride is 0.763 part, the weight part of the thiourea is 1.439 part, and the weight part of the citric acid is 2.174 parts.
Preferably, in the step (1), the weight part of the hydrated sodium molybdate is 0.303 part, the weight part of the hydrated tin chloride is 0.572 part, the weight part of the thiourea is 1.304 part, and the weight part of the citric acid is 1.725 part.
Has the advantages that: 1T @2H-MoS prepared by the invention2/SnS2The 60-minute degradation rate of the heterogeneous compound for degrading MB reaches 75.3%.
Preferably, in the step (1), the weight part of the hydrated sodium molybdate is 0.454 part, the weight part of the hydrated tin chloride is 0.381 part, the weight part of the thiourea is 1.17 part, and the weight part of the citric acid is 1.276 part.
Preferably, in the step (1), the weight parts of the hydrated sodium molybdate are 0.605 part, the weight parts of the hydrated tin chloride are 0.191 part, the weight parts of the thiourea are 1.035 part, and the weight parts of the citric acid are 0.827 part.
Preferably, the stirring in step (1) includes ultrasonic stirring and magnetic stirring.
Preferably, the step (3) is performed by alternately washing with ethanol and distilled water.
Preferably, the centrifugally washed product is dried in vacuum at 60 ℃ for 8h in the step (3).
The invention also provides 1T @ 2H-MoS prepared by the preparation method2/SnS2The visible light is responsive to the photocatalyst.
Has the advantages that: 1T @2H-MoS prepared by adopting preparation method disclosed by the invention2/SnS2The heterogeneous composite has 1T-MoS2And 2H-MoS2Two lattices, small size spherical MoS2SnS attached to large scale2On the nano-sheet. The prepared 1T @2H-MoS2/SnS2The heterogeneous compound has good photocatalytic degradation performance, and has good stability and recyclability.
The invention also provides 1T @ 2H-MoS prepared by the preparation method2/SnS2The visible light response photocatalyst is applied to degrading methylene blue and rhodamine B.
Has the advantages that: the photocatalyst prepared by the invention has visible light responsiveness, has photodegradation capability on methylene blue and rhodamine B under visible light irradiation, and has photodegradation capability obviously superior to MoS with single component2And SnS2。
The invention has the advantages that: the invention adopts a one-step synthesis method to prepare the product, the preparation method is simple, the invention firstly mixes hydrated sodium molybdate and hydrated tin chloride, then thiourea is added, and the mol ratio of Mo and Sn and MoS are controlled2The proportion of the two phases in the mixed phase is such that 1T-MoS2、2H-MoS2And SnS2A synergistic effect is generated.
1T @2H-MoS prepared by adopting preparation method disclosed by the invention2/SnS2The heterogeneous compound is in a mixed state of a 1T metal phase and a 2H semiconductor phase, and the small-size spherical MoS2SnS attached to large scale2On the nano-sheet. The prepared 1T @2H-MoS2/SnS2The heterogeneous compound has good photocatalytic degradation performance, and has good stability and recyclability.
Small size MoS2More exposed edges and active sites and high conductivity of the 1T metal phase in the mixed phase, 1T @2H-MoS2/SnS2The heterostructure not only increases the absorption of visible light, but also promotes the separation and migration of electron-hole pairs, and improves the photocatalytic efficiency.
The addition of citric acid is intended to maintain an acidic solution environment, so that Mo and Sn can be effectively prevented from being oxidized, and the addition amount of citric acid needs to be strictly controlled to control the pH value of the solution to be between 3 and 5. If citric acid is not present, the final synthesis product of the Sn source is SnO2Instead of SnS2Even further contains a certain amount of MoO3。
Drawings
FIG. 1 is an XRD pattern of a single component material of a composite sample of examples 1 to 4 of the present invention, comparative example 1 and comparative example 2;
FIG. 2 is a Raman spectrum of a single component material in a composite sample of examples 1 to 4 of the present invention, comparative example 1, and comparative example 2;
FIG. 3 is a full spectrum of the product MSS40 in example 2 of the present invention after XPS characterization;
FIG. 4 is an XPS high resolution plot of Mo3d energy level for the product MSS40 in example 2;
FIG. 5 is a graph of pure MoS of comparative example 2 of the present invention2SEM picture of (1);
FIG. 6 shows pure SnS of comparative example 1 of the present invention2SEM picture of (1);
FIG. 7 is an SEM image of product MSS40 of example 2 according to the invention;
figure 8 is a low resolution TEM image of product MSS40 of example 2 of the present invention;
FIG. 9 is a graph of the resolved HTEM of product MSS40 in example 2 of the present invention;
FIG. 10 is an enlarged view of the area within the box of FIG. 9;
FIG. 11 is a graph showing the photocatalytic degradation MB of a single component material in a composite sample of examples 1 to 4 of the present invention, comparative examples 1 and 2;
figure 12 is a graph of the efficiency of the product MSS40 cycle degradation of MB solution in example 2 of the present invention;
FIG. 13 is a graph showing the results of the photocatalytic degradation RhB of the single component materials in the composite samples of examples 1 to 4 of the present invention, comparative examples 1 and 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Tin chloride hydrate (SnCl) in the examples below4.5H2O), sodium molybdate hydrate (Na)2MoO4.2H2O), thiourea (CH)4N2S) and citric acid (C)6H8O7) The purity of the product is more than 99 percent, and the product is provided by Shanghai Merlin chemical reagent company.
Example 1
1T@2H-MoS2/SnS2The preparation method of the visible light response photocatalyst comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.151g of sodium molybdate hydrate and 0.763g of stannic chloride hydrate in 80mL of deionized water, then adding 2.174g of citric acid and 1.439g of thiourea, carrying out ultrasonic treatment, and magnetically stirring at room temperature for 1h for dissolution, wherein the pH value of the solution is 3-5;
(2) hydrothermal synthesis: transferring the solution in the step (1) to a 100mL reaction kettle, heating to 220 ℃, preserving heat for 24 hours, and naturally cooling to room temperature;
(3) separation and washing: collecting the reaction product in the step (2), centrifuging, alternately washing with ethanol and distilled water to remove impurities, and then vacuum drying at 60 ℃ for 8h to obtain MoS2Respectively has a mass ratio of 20 percent of 1T @2H-MoS2/SnS2Photocatalyst, named MSS 20.
Example 2
1T@2H-MoS2/SnS2The preparation method of the visible light response photocatalyst comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.303g of sodium molybdate hydrate and 0.572g of stannic chloride hydrate in 80mL of deionized water, then adding 1.725g of citric acid and 1.304g of thiourea, carrying out ultrasonic treatment, and magnetically stirring at room temperature for 1h for dissolution, wherein the pH value of the solution is 3-5;
(2) hydrothermal synthesis: transferring the solution in the step (1) to a 100mL reaction kettle, heating to 220 ℃, preserving heat for 24 hours, and naturally cooling to room temperature;
(3) separation and washing: collecting the reaction product in the step (2), centrifuging, alternately washing with ethanol and distilled water to remove impurities, and then vacuum drying at 60 ℃ for 8h to obtain MoS2Respectively has a mass ratio of 40 percent of 1T @2H-MoS2/SnS2Photocatalyst, named MSS 40.
Example 3
1T@2H-MoS2/SnS2The preparation method of the visible light response photocatalyst comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.454g of sodium molybdate hydrate and 0.381g of stannic chloride hydrate in 80mL of deionized water, then adding 1.276g of citric acid and 1.17g of thiourea, carrying out ultrasonic treatment, and magnetically stirring at room temperature for 1h for dissolution, wherein the pH value of the solution is 3-5;
(2) hydrothermal synthesis: transferring the solution in the step (1) to a 100mL reaction kettle, heating to 220 ℃, preserving heat for 24 hours, and naturally cooling to room temperature;
(3) separation and washing: collecting the reaction product in the step (2), centrifuging, alternately washing with ethanol and distilled water to remove impurities, and then vacuum drying at 60 ℃ for 8h to obtain MoS2Respectively has a mass ratio of 60 percent of 1T @2H-MoS2/SnS2Photocatalyst, named MSS 60.
Example 4
1T@2H-MoS2/SnS2The preparation method of the visible light response photocatalyst comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.605g of sodium molybdate hydrate and 0.191g of stannic chloride hydrate in 80mL of deionized water, then adding 0.827g of citric acid and 1.035g of thiourea, carrying out ultrasonic treatment, and magnetically stirring at room temperature for 1h for dissolution, wherein the pH value of the solution is 3-5;
(2) hydrothermal synthesis: transferring the solution in the step (1) to a 100mL reaction kettle, heating to 220 ℃, preserving heat for 24 hours, and naturally cooling to room temperature;
(3) separation and washing: collecting the reaction product in the step (2), centrifuging, alternately washing with ethanol and distilled water to remove impurities, and then vacuum drying at 60 ℃ for 8h to obtain MoS2Respectively has a mass ratio of 1T @2H-MoS of 80%2/SnS2Photocatalyst, named MSS 80.
Comparative example 1
Single component SnS2The preparation method comprises the following steps: 0.349g SnCl4·5H2O and 0.96g citric acid were dissolved in 40ml distilled water. 0.576g of thiourea was poured into the above solution and stirred for 30 minutes. The final solution was transferred to a 50ml autoclave and heated at 180 ℃ for 12 hours. Subsequently, the sample was centrifuged and washed several times with ethanol and distilled water alternately to remove impurities, and then dried in vacuum at 60 ℃ for 8 hours to obtain SnS2Nanosheets.
Comparative example 2
Single-component MoS2The preparation method comprises the following steps: 0.242g Na2MoO4·2H2O and 0.288g of thiourea were dissolved in 10ml of distilled water, and then 0.15g of citric acid was dissolved in 5ml of distilled water, and then the above solution was poured and stirred magnetically 3And 0 minute. The final solution was transferred to a 50ml reaction kettle and heated at 220 ℃ for 24 h. Subsequently, the black product was centrifuged and washed several times with ethanol and distilled water alternately to remove impurities, and then dried in vacuum at 60 ℃ for 8 hours to obtain black MoS2And (3) powder.
Example 5
The structures and properties of the composite samples of examples 1 to 4, and the single component materials of comparative examples 1 and 2 were measured.
FIG. 1 is XRD patterns of the single component materials of the composite samples of examples 1 to 4, comparative examples 1 and 2, and it can be seen that SnS is contained in the composite material2Easy to identify, MoS2Phases cannot be reflected from the XRD pattern because of the small crystal size.
FIG. 2 is a Raman spectrum of the single component materials of the composite samples of examples 1 to 4, comparative examples 1 and 2, by which not only MoS can be identified2It is also possible to distinguish between the 1T and 2H phase components contained therein.
Fig. 3 and 4 are the results of XPS characterization of the product MSS40 in example 2. Wherein, FIG. 3 is XPS full spectrum, which proves that the sample contains four constituent elements of Sn, Mo, S and O, FIG. 4 is Mo3d energy level XPS high resolution spectrum, the position and distance of the cleavage peak prove that +4 valence Mo has two lattice environments, which respectively correspond to MoS of 1T phase and 2H phase2In which MoS of 1T phase2Account for MoS2The mass ratio of (B) was 61.5%.
FIG. 5 is a pure MoS2The SEM image of (A) shows a hollow nano spherical structure, and the diameter of the sphere is 2 mu m; FIG. 6 shows pure SnS2The SEM image shows a hexagonal nano sheet structure, and the transverse dimension is about 600 nm; FIG. 7 is an SEM image of a composite sample MSS40, representing a spherical MoS of small size2(100-200nm) SnS attached to a large scale (600nm)2Shows MoS in one-step synthesis process2The size becomes smaller; FIG. 8 is a low resolution TEM picture of MSS40 of a composite sample, showing MoS2Is a folded spherical MoS with small size2Successful attachment of nanospheres to SnS2The size of the surface is consistent with that observed by SEM; FIG. 9 shows MSS40 of composite sampleHigh resolution HTEM pictures with spots showing hexagonal symmetry in their fast fourier transforms indicate excellent crystalline quality and excellent interfacial coupling of the samples, from which it is clear that 1T-MoS2And 2H-MoS2Two lattices. Fig. 10 is an enlarged view of the area in fig. 9, where two lattice fringe spacings can be clearly measured. Small size MoS2More exposed edges and active sites and high conductivity of the 1T metal phase in the mixed phase, 1T @2H-MoS2/SnS2The heterostructure not only increases the absorption of visible light, but also promotes the separation and migration of electron-hole pairs, and improves the photocatalytic efficiency.
The prepared product is subjected to photocatalytic performance test, and the test method comprises the following steps:
the prepared photocatalyst is respectively irradiated by a xenon lamp simulating sunlight with 350W for 120 minutes to degrade 100mL of Methylene Blue (MB) solution with the concentration of 10mg/L or 15mg/L of rhodamine B (RhB).
The test results were as follows:
FIG. 11 is a graph of MB degradation by photocatalysis of different samples, wherein the MB degradation rate reaches 75.3% in 60 minutes and 92.1% in 120 minutes, which exceeds the two-dimensional surface-to-surface contact 2H-MoS reported by Zhang et al (J.Alloy.Compd.775(2019)726-2/SnS2A degradation rate of up to 58% in the heterojunction. Fig. 12 shows the efficiency of MSS40 in degrading MB solution over multiple cycles, and maintains good photocatalytic activity over four cycles, indicating that MSS40 has good stability and recyclability.
FIG. 13 is a graph showing the photocatalytic degradation RhB of different samples, wherein the RhB degradation rate reaches 88.4% after 60 minutes of illumination and reaches 95.3% after 120 minutes of illumination from the time 0. The 30 minutes before the time 0 in the figure corresponds to the dark room treatment, which shows that the adsorption is large, and the degradation effect of the product on MB is better than that of RhB in view of combining the data of the adsorption and the photocatalysis.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. 1T @2H-MoS2/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing and preparing liquid: dissolving 0.151-0.605 part of hydrated sodium molybdate and 0.191-0.763 part of hydrated tin chloride in deionized water, then adding citric acid and 1.035-1.439 parts of thiourea, stirring and dissolving, and then, the pH value of the solution is 3-5;
(2) hydrothermal synthesis: heating the solution in the step (1) to 220 ℃, preserving heat for 24 hours, and cooling to room temperature;
(3) separation and washing: centrifuging the reaction product in the step (2), washing and drying to obtain 1T @2H-MoS2/SnS2A photocatalyst.
2. 1T @2H-MoS according to claim 12/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: the weight fraction of the added citric acid is 0.827-2.174 parts, and the added deionized water is 80 mL.
3. 1T @2H-MoS according to claim 22/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: in the step (1), the weight parts of the sodium molybdate hydrate, the tin chloride hydrate, the thiourea and the citric acid are respectively 0.151, 0.763, 1.439 and 2.174, respectively.
4. 1T @2H-MoS according to claim 22/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: in the step (1), the weight parts of sodium molybdate hydrate, tin chloride hydrate, thiourea and citric acid are respectively 0.303, 0.572, 1.304 and 1.725 respectively。
5. 1T @2H-MoS according to claim 22/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: in the step (1), the weight parts of the sodium molybdate hydrate are 0.454, the weight parts of the stannic chloride hydrate are 0.381, the weight parts of the thiourea are 1.17, and the weight parts of the citric acid are 1.276.
6. 1T @2H-MoS according to claim 22/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: in the step (1), the weight parts of the hydrated sodium molybdate are 0.605, the weight parts of the hydrated tin chloride are 0.191, the weight parts of the thiourea are 1.035, and the weight parts of the citric acid are 0.827.
7. 1T @2H-MoS according to claim 12/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: the stirring in the step (1) includes ultrasonic stirring and magnetic stirring.
8. 1T @2H-MoS according to claim 12/SnS2The preparation method of the visible light response photocatalyst is characterized by comprising the following steps: and (3) alternately washing by using ethanol and distilled water.
9. 1T @2H-MoS prepared by the preparation method of any one of claims 1 to 82/SnS2The visible light is responsive to the photocatalyst.
10. 1T @2H-MoS prepared by the preparation method of any one of claims 1 to 82/SnS2The visible light response photocatalyst is applied to degrading methylene blue and rhodamine B.
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