CN114682274B - S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst - Google Patents
S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst Download PDFInfo
- Publication number
- CN114682274B CN114682274B CN202210397931.4A CN202210397931A CN114682274B CN 114682274 B CN114682274 B CN 114682274B CN 202210397931 A CN202210397931 A CN 202210397931A CN 114682274 B CN114682274 B CN 114682274B
- Authority
- CN
- China
- Prior art keywords
- znin
- snse
- rich
- defect
- rich defect
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000007547 defect Effects 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002800 charge carrier Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910052711 selenium Inorganic materials 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 7
- 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 6
- 238000013112 stability test Methods 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002091 nanocage Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst, which belongs to the technical field of photocatalysis. The invention uses self-made S-rich defect ZnIn 2 S 4 、SnCl 4 ·5H 2 O and Se powder are used as raw materials, and S-rich defect ZnIn is prepared by a one-step hydrothermal method 2 S 4 /SnSe 2 Ohmic junction photocatalyst. Due to ZnIn 2 S 4 And SnSe 2 Matched energy band and crystal structure, plus S-rich defect ZnIn 2 S 4 Surface-rich coordinated unsaturated S atom and SnSe 2 In the S-rich defect ZnIn 2 S 4 The surface is tightly combined through forming an interface Sn-S bond, thereby forming ohmic contact and promoting ZnIn 2 S 4 On photo-generated electron to SnSe 2 The photocatalyst can be used for producing hydrogen by decomposing water, and the hydrogen production rate of the water under the irradiation of visible light reaches 25-29 mmol.g ‑1 ·h ‑1 The hydrogen production rate is reduced by about 4% after the above-mentioned method is repeated for 6 times.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and in particular relates to an S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst.
Background
The rapid development of global economy and the improvement of human living standards have led to an increasing global energy demand. Meanwhile, the human society has to face two major problems of energy shortage and ecological pollution, so the development and utilization of novel energy, especially clean energy, is crucial to breaking through the energy and environmental dilemma facing the human society at present. The photocatalytic water splitting hydrogen production can convert renewable solar energy into hydrogen energy, so that the limitation on fossil energy is eliminated, any harmful pollutant is not discharged in the whole reaction process, and the method is considered to be an optimal energy conversion technology and is expected to simultaneously relieve the problems of energy shortage and environmental pollution. However, the purpose isThe development of photocatalysis technology still remains in the experimental stage, and the main difficulty is the lack of efficient photocatalysis materials. Among the many photocatalytic materials developed, the multi-metal sulfide semiconductor ZnIn 2 S 4 Due to the proper adjustable energy band structure, excellent visible light absorption performance and light stability, the light-emitting diode is heated by researchers in various countries. Of course, a single ZnIn 2 S 4 The photocatalytic water splitting hydrogen production performance is not satisfactory, and the main problem is that the separation efficiency of photogenerated charge carriers is insufficient. To solve this problem, noble metals such as Pt, pd, ag-Pd alloys, etc. are used to modify ZnIn 2 S 4 In order to improve the separation efficiency of the photo-generated carriers, although a better effect is obtained, the expensive price and the rare content of the noble metal make the modification strategy not widely applied. Thus, transition metal compounds have also been developed for use as ZnIn 2 S 4 For example, xu et al will MoS 2 Modification of ZnIn as a promoter 2 S 4 As a result, it was found that MoS 2 -ZnIn 2 S 4 The hydrogen production performance of the photocatalytic water splitting is higher than that of single ZnIn 2 S 4 The performance of (a) is improved by 7 times (Tan C L, qi M Y, tang Z R, xu Y J, applied Catalysis B: environmental 298 (2021) 120541). Dai et al prepared hollow Co 2 P nano cage and modifying the P nano cage in ZnIn 2 S 4 Surface, hydrogen production result shows that Co 2 P/ZnIn 2 S 4 The hydrogen rate of the decomposed water reaches 7.93mmol/g/h, which is far higher than that of single ZnIn 2 S 4 Photocatalyst, and higher than noble metal Pt modified ZnIn 2 S 4 (Zhang Q, wang X H, zhang J H, li L F, gu H J, dai W L, journal of Colloid and Interface Science 590 (2021) 632-640). A number of studies have found that transition metal compounds with a narrow band gap are useful as ZnIn 2 S 4 The promoter achieves good effect.
SnSe 2 Also a narrow bandgap transition metal chalcogenide having excellent visible light absorption properties, the narrower bandgap of which imparts metal-like properties thereto. First, from the crystal structure, snSe 2 With ZnIn 2 S 4 Belonging to the same space group: p-3m1 (164), and their unit cell parameters are also very close (SnSe 2 :α=β=90°,γ=120°;ZnIn 2 S 4 :/>α=β=90°, γ=120°. Similar crystal structures illustrate that a tightly bound heterogeneous interface is very easy to form between the two. In addition, from the energy band structure, snSe 2 Work function of about 5.3eV, less than ZnIn 2 S 4 5.88eV of (B), explaining that when ZnIn 2 S 4 With SnSe 2 After close contact, snSe 2 Free electrons on the ZnIn will transfer to 2 S 4 In the method, znIn 2 S 4 Is bent downward to form a specific ohmic-like contact. In this case, znIn 2 S 4 The photo-generated electrons generated on the guide belt are smoothly transferred to the SnSe 2 Thereby leading to ZnIn 2 S 4 The separation efficiency of the photo-generated charge carriers in the catalyst is effectively improved, and finally the ZnIn is hopeful to be realized 2 S 4 The photocatalytic performance of the catalyst is obviously improved. However, there have been no reports.
In conclusion, the invention has the advantages of enriching the S defect ZnIn 2 S 4 In-situ growth of SnSe on surface by hydrothermal method 2 And (3) a cocatalyst. Obtaining the S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst. Due to ZnIn 2 S 4 And SnSe 2 Matched energy band structure and crystal structure, and S-rich defect ZnIn 2 S 4 Surface-rich coordinated unsaturated S atom and SnSe 2 In ZnIn 2 S 4 The surface is tightly combined through forming an interface Sn-S bond, thereby forming special ohmic contact, and promoting ZnIn 2 S 4 On photo-generated electron to SnSe 2 The transfer is performed, so that the high-efficiency hydrogen production performance by decomposing water is realized, and the method has a large practical application prospect.
Disclosure of Invention
The invention aims to provide a ZnIn rich in S defect 2 S 4 /SnSe 2 The ohmic junction photocatalyst has excellent hydrogen production performance by photocatalytic decomposition of water.
The aim of the invention is achieved by the following technical scheme:
(1) S-rich defect ZnIn 2 S 4 /SnSe 2 Preparation of ohmic junction photocatalyst
SnCl is added 4 ·5H 2 S-rich defect ZnIn with O concentration of 0.91-2 mM 2 S 4 Fully mixing the dispersion liquid and Se hydrazine hydrate solution with Se concentration of 28.86-63.8 mM according to the volume ratio of 8:1, preserving heat for 3-7 hours at 160-200 ℃ in a polytetrafluoroethylene reaction kettle, cooling to room temperature, centrifuging to precipitate, sequentially washing with deionized water and ethanol, and vacuum drying at 60 ℃ to obtain S-rich defect ZnIn 2 S 4 /SnSe 2 Under the irradiation of visible light, the ohmic junction photocatalyst can decompose water to produce hydrogen at a rate of 25-29 mmol.g -1 ·h -1 And after repeated use for 6 times, the hydrogen production rate is reduced by about 4%.
(2) S-rich defect ZnIn 2 S 4 /SnSe 2 Hydrogen production performance test for decomposed water of ohmic junction photocatalyst
Weighing 5mg of the prepared S-enriched defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst, ultrasonically dispersed into 100mL of aqueous solution with ascorbic acid concentration of 0.1M, then the dispersion was transferred into a 250mL photocatalytic reactor and the reaction system was evacuated while preheating a light source (300W Xe lamp +420nm cut-off filter). Then, the light source was moved to just above the reactor to start the photocatalytic reaction, and the produced gas was measured for hydrogen production by gas chromatography and the hydrogen production rate was calculated.
(3) S-rich defect ZnIn 2 S 4 /SnSe 2 Test of hydrogen circulation stability of decomposed water of ohmic junction photocatalyst
After the photocatalytic reaction in the step (2) is finished, 1g of ascorbic acid sacrificial agent is added, and after dissolution, the photocatalytic decomposition of the water to produce hydrogen reaction is restarted. The above procedure was repeated 5 times in total.
The invention discloses a ZnIn rich in S defect 2 S 4 /SnSe 2 Compared with the existing photocatalyst, the ohmic junction photocatalyst has the advantages that:
(1) In the invention, the prepared photocatalyst is a catalyst prepared from S-rich defect ZnIn 2 S 4 And SnSe 2 Novel ohmic junction photocatalytic materials bonded by interfacial Sn-S bonds.
(2) In the invention, under the combined action of an ohmic junction, a built-in electric field, a compact interface contact and an S vacancy, the S defect ZnIn is enriched 2 S 4 The photo-generated electrons generated on the guide belt are rapidly transferred to SnSe 2 On top of that, znIn is promoted 2 S 4 Separation of the charge carriers generated by mid-light, thereby causing S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production rate of the ohmic junction photocatalyst under the irradiation of visible light reaches 25-29 mmol.g after decomposing water -1 ·h -1 。
Drawings
FIG. 1 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 Electron paramagnetic resonance spectrogram of ohmic junction photocatalyst;
FIG. 2 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 Scanning electron microscope pictures of ohmic junction photocatalysts;
FIG. 3 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 Transmission of ohmic junction photocatalyst and high resolution transmission electron microscope photograph;
FIG. 4 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 S2p XPS spectrum of ohmic junction photocatalyst;
FIG. 5 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of a decomposition water hydrogen production performance map;
FIG. 6 shows the S-rich defect ZnIn prepared in example 1 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of a decomposition water hydrogen circulation stability test chart;
FIG. 7 is a diagram showing the S-rich defect ZnIn prepared in example 2 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of a decomposition water hydrogen production performance map;
FIG. 8 is a S-rich defect ZnIn prepared in example 2 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of a decomposition water hydrogen circulation stability test chart;
FIG. 9 is a S-rich defect ZnIn prepared in example 3 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of a decomposition water hydrogen production performance map;
FIG. 10 shows the S-rich defect ZnIn prepared in example 3 2 S 4 /SnSe 2 Visible light (lambda) of ohmic junction photocatalyst>420 nm) of the decomposed water hydrogen circulation stability test chart.
Detailed Description
The present invention will be described in detail below with reference to the drawings and the specific embodiments, which are only examples, and do not limit the scope of the present invention in any way.
Example 1
Weigh 0.0089g SnCl 4 ·5H 2 O was added to 20mL of deionized water, to which 100mg of homemade S-rich defect ZnIn was added 2 S 4 Ultrasonic dispersing for 1 hour; meanwhile, 0.008g Se powder is weighed and added into 2.5mL of hydrazine hydrate, and the mixture is dissolved in water bath at 80 ℃; then, adding Se hydrazine hydrate solution into the above-mentioned ZnSin containing S-rich defect 2 S 4 And SnCl 4 ·5H 2 Mixing and stirring the mixture of O for 30 minutes; finally, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, preserving heat for 5 hours in a baking oven at 180 ℃, cooling to room temperature, centrifugally separating, washing and precipitating with deionized water and ethanol in sequence, and finally vacuum drying at 60 ℃ to obtain the S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst. The electron paramagnetic resonance spectrum is shown in figure 1 of the drawings in the specification. As can be seen from FIG. 1, the prepared photocatalyst showed strong electron paramagnetic resonance response corresponding to the S defect, which proves that the prepared photocatalyst did contain the full scaleRich S defects. The scanning electron microscope photo is shown in figure 2 of the drawings in the specification. As can be seen from FIG. 2, the S-rich defect ZnIn 2 S 4 /SnSe 2 The ohmic junction photocatalyst presents a multi-level micron flower ball shape. The transmission and high resolution transmission electron microscope photo is shown in figure 3 in the drawings of the specification. Fig. 3 (a) is consistent with the results of fig. 1. From FIG. 3 (b), two different lattice fringes can be observed, wherein a lattice fringe having a interplanar spacing of 0.32nm corresponds to hexagonal ZnIn 2 S 4 In ZnIn (102) crystal face 2 S 4 Above the lattice fringes, a lattice fringe having a lattice spacing of about 0.19nm was observed, which corresponds to hexagonal SnSe 2 The simultaneous occurrence of lattice fringes in the (110) crystal face of (a) proves that the S-rich defect ZnIn 2 S 4 /SnSe 2 Successful preparation of the photocatalyst, in addition, the lattice fringes of intimate contact between the two also indicate the S-rich defect ZnIn 2 S 4 With SnSe 2 And tightly bonded with each other. The S2p XPS spectrum is shown in figure 4 of the specification. As can be seen from FIG. 4, a clear correspondence to SnS can be observed at binding energies of 161.25 and 162.54eV 2 The S2p peak in (b) shows SnSe 2 Sn atoms and S-rich defects ZnIn 2 S 4 The chemical interaction between S atoms in the SnSe is proved 2 Growth of ZnSn rich in S defects by interfacial Sn-S bonds 2 S 4 A surface. Visible light (lambda)>420 nm) of the hydrogen production performance of the decomposed water is shown in figure 5 in the specification. As can be seen from FIG. 5, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production rate of the ohmic junction photocatalyst under visible light reaches 29.34 mmol.g -1 ·h -1 . Visible light (lambda)>420 nm) of the decomposed water hydrogen circulation stability test chart is shown in figure 6 of the specification. As can be seen from FIG. 6, after 6 consecutive re-uses, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production performance of the ohmic junction photocatalyst is only reduced by 4.2 percent.
Example 2
Weigh 0.0064g SnCl 4 ·5H 2 O was added to 20mL of deionized water, to which 100mg of homemade S-rich defect ZnIn was added 2 S 4 Ultrasound for 1 hourDispersing; meanwhile, 0.0057g Se powder is weighed and added into 2.5mL of hydrazine hydrate, and the mixture is dissolved in water bath at 80 ℃; then, adding Se hydrazine hydrate solution into the above-mentioned ZnSin containing S-rich defect 2 S 4 And SnCl 4 ·5H 2 Mixing and stirring the mixture of O for 30 minutes; finally, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, preserving heat for 3 hours in a baking oven at 200 ℃, cooling to room temperature, sequentially washing and precipitating with centrifugal separation, deionized water and ethanol, and finally vacuum drying at 60 ℃ to obtain the S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst. Visible light (lambda)>420 nm) of the hydrogen production performance of the decomposed water is shown in figure 6 in the specification. As can be seen from FIG. 7, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production rate of the ohmic junction photocatalyst under visible light reaches 27.39 mmol.g -1 ·h -1 . Visible light (lambda)>420 nm) of the decomposed water hydrogen circulation stability test chart is shown in figure 8 of the specification. As can be seen from FIG. 8, after 6 consecutive re-uses, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production performance of the ohmic junction photocatalyst is only reduced by 3.7 percent.
Example 3
Weigh 0.014g SnCl 4 ·5H 2 O was added to 20mL of deionized water, to which 100mg of homemade S-rich defect ZnIn was added 2 S 4 Ultrasonic dispersing for 1 hour; meanwhile, 0.0126g Se powder is weighed and added into 2.5mL of hydrazine hydrate, and the mixture is dissolved in water bath at 80 ℃; then, adding Se hydrazine hydrate solution into the above-mentioned ZnSin containing S-rich defect 2 S 4 And SnCl 4 ·5H 2 Mixing and stirring the mixture of O for 30 minutes; finally, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, preserving heat for 4 hours in a baking oven at 170 ℃, cooling to room temperature, sequentially washing and precipitating with centrifugal separation, deionized water and ethanol, and finally vacuum drying at 60 ℃ to obtain the S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst. Visible light (lambda)>420 nm) of the hydrogen production performance of the decomposed water is shown in figure 9 in the specification. As can be seen from FIG. 9, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production rate of the ohmic junction photocatalyst under visible light reaches 25.01 mmol.g -1 ·h -1 . Visible light (lambda)>420 nm) of the decomposed water hydrogen circulation stability test chart is shown in figure 10 of the specification. From fig. 10. It can be seen that after 6 consecutive repeated uses, the S-rich defect ZnIn 2 S 4 /SnSe 2 The hydrogen production performance of the ohmic junction photocatalyst is only reduced by 4.4 percent.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (2)
1. S-rich defect ZnIn 2 S 4 /SnSe 2 An ohmic junction photocatalyst, characterized in that the photocatalyst comprises SnSe 2 In-situ growth is performed on the S-rich defect ZnIn 2 S 4 The surface and the two are combined through Sn-S chemical bond, and the preparation method is as follows: weigh 0.0089g SnCl 4 ·5H 2 O was added to 20mL of deionized water, to which 100mg of homemade S-rich defect ZnIn was added 2 S 4 Ultrasonic dispersing for 1 hour; meanwhile, 0.008g Se powder is weighed and added into 2.5mL of hydrazine hydrate, and the mixture is dissolved in water bath at 80 ℃; then, adding Se hydrazine hydrate solution into the above-mentioned ZnSin containing S-rich defect 2 S 4 And SnCl 4 ·5H 2 Mixing and stirring the mixture of O for 30 minutes; finally, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, preserving heat for 5 hours in a baking oven at 180 ℃, cooling to room temperature, centrifugally separating, washing and precipitating with deionized water and ethanol in sequence, and finally vacuum drying at 60 ℃ to obtain the S-rich defect ZnIn 2 S 4 /SnSe 2 Ohm-junction photocatalyst, which under the irradiation of visible light, has a hydrogen production rate of 29.34 mmol.g by decomposing water -1 ·h -1 And after repeated use for 6 times, the hydrogen production rate is reduced by only 4.2%.
2. An S-rich defect ZnIn as claimed in claim 1 2 S 4 /SnSe 2 An ohmic junction photocatalyst characterized by being rich in S defect ZnIn 2 S 4 With SnSe 2 Ohmic contact between them and built-in electric field to promote S-rich defect ZnIn 2 S 4 Photogeneration on a guide stripElectron transfer to SnSe 2 On the one hand, the S-rich defect ZnIn is obviously improved 2 S 4 And the separation efficiency of photo-generated charge carriers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210397931.4A CN114682274B (en) | 2022-04-08 | 2022-04-08 | S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210397931.4A CN114682274B (en) | 2022-04-08 | 2022-04-08 | S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114682274A CN114682274A (en) | 2022-07-01 |
CN114682274B true CN114682274B (en) | 2023-11-17 |
Family
ID=82142398
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210397931.4A Active CN114682274B (en) | 2022-04-08 | 2022-04-08 | S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114682274B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109569657A (en) * | 2019-01-04 | 2019-04-05 | 中国计量大学 | One kind is rich in surface sulphur vacancy defect state structure sulfur-indium-zinc photochemical catalyst and preparation method thereof |
CN109661735A (en) * | 2016-06-28 | 2019-04-19 | 纳米技术有限公司 | Organic/inorganic mixing el light emitting device with two-dimensional material emission layer |
CN110961123A (en) * | 2019-12-21 | 2020-04-07 | 青岛科技大学 | All-solid-state direct Z-type ZnIn prepared by hydrothermal method2S4-MoSe2High-efficiency photocatalyst |
CN113171780A (en) * | 2021-05-08 | 2021-07-27 | 青岛科技大学 | Molybdenum selenide/defect-rich sulfur-indium-zinc/cadmium selenide double-Z-shaped catalyst for photocatalytic water splitting hydrogen production |
-
2022
- 2022-04-08 CN CN202210397931.4A patent/CN114682274B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109661735A (en) * | 2016-06-28 | 2019-04-19 | 纳米技术有限公司 | Organic/inorganic mixing el light emitting device with two-dimensional material emission layer |
CN109569657A (en) * | 2019-01-04 | 2019-04-05 | 中国计量大学 | One kind is rich in surface sulphur vacancy defect state structure sulfur-indium-zinc photochemical catalyst and preparation method thereof |
CN110961123A (en) * | 2019-12-21 | 2020-04-07 | 青岛科技大学 | All-solid-state direct Z-type ZnIn prepared by hydrothermal method2S4-MoSe2High-efficiency photocatalyst |
CN113171780A (en) * | 2021-05-08 | 2021-07-27 | 青岛科技大学 | Molybdenum selenide/defect-rich sulfur-indium-zinc/cadmium selenide double-Z-shaped catalyst for photocatalytic water splitting hydrogen production |
Non-Patent Citations (1)
Title |
---|
Chun Du et al.."Promoting photocatalytic hydrogen evolution by introducing hot islands: SnSe nanoparticles on ZnIn2S4 monolayer".《Chemical Engineering Journal》.2020,第404卷第126477(1-8)页. * |
Also Published As
Publication number | Publication date |
---|---|
CN114682274A (en) | 2022-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108855167B (en) | Carbon-doped TiO2Nano multilevel structure material and application thereof | |
CN113351210B (en) | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction | |
CN113751028A (en) | Organic-inorganic hybrid photocatalytic hydrogen evolution material and preparation method and application thereof | |
CN115845886B (en) | CdSe/MXene composite photocatalyst and preparation method and application thereof | |
CN112717958B (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
CN114682274B (en) | S-rich defect ZnIn 2 S 4 /SnSe 2 Ohmic junction photocatalyst | |
CN110252359B (en) | Preparation method of catalyst for photolysis of water to produce hydrogen by using cadmium sulfide-containing heterojunction | |
CN114602509B (en) | S-rich defect ZnIn 2 S 4 /In 2 Se 3 Heterojunction photocatalyst and application thereof | |
CN100351015C (en) | Method for preparing photocatalyst of platinum-carried cadmium sulfide | |
Xu et al. | Efficient Visible Light Hydrogen Evolution Catalyst Composed of Non-noble Metal Nitride (Ni3N) Cocatalyst and Zn0. 5Cd0. 5S Solid Solution | |
Gemeda et al. | A recent review on photocatalytic CO2 reduction in generating sustainable carbon-based fuels | |
CN110124650B (en) | graphene/TiO2Compound, preparation method and method for catalyzing water decomposition to produce hydrogen by using compound as catalyst | |
CN114471735A (en) | Nickel complex/TiO2Composite material and preparation method and application thereof | |
CN102423715A (en) | Preparation method for graphene composite photocatalyst with CdS a TaON core-shell structure, and application thereof | |
CN114797905B (en) | High-efficiency ZnIn 2 S 4 /SnSe 2 /In 2 Se 3 Catalyst for producing hydrogen by photolysis of water | |
CN111111738A (en) | Composite photocatalytic material and preparation method thereof | |
CN114713247B (en) | Nickel-coated sulfur-manganese-cadmium plasma photocatalyst rich in sulfur vacancy and preparation method and application thereof | |
CN116371425B (en) | CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst | |
CN115193466B (en) | Bimetallic hydrogen evolution catalyst and preparation method thereof | |
CN114570405B (en) | Preparation method and application of two-dimensional mesoporous tantalum nitride photocatalytic material | |
CN115400771B (en) | Ni prepared by one-step solvothermal method 12 P 5 /In(OH) 3 /CdIn 2 S 4 Ternary composite catalyst | |
CN115608380B (en) | Preparation method of transition metal sulfide with exposed interlayer metal | |
CN109794270B (en) | V-shaped groove2O5Preparation method of/BiOI semiconductor composite photocatalyst | |
CN117654553A (en) | Ni deposition of ZnIn 2 S 4 Is prepared by the preparation method of (2) | |
CN117181220A (en) | Ternary composite photocatalyst Au/Ti 3 C 2 /2D-C 3 N 4 Preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |