CN110560105A - Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production - Google Patents
Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production Download PDFInfo
- Publication number
- CN110560105A CN110560105A CN201910825822.6A CN201910825822A CN110560105A CN 110560105 A CN110560105 A CN 110560105A CN 201910825822 A CN201910825822 A CN 201910825822A CN 110560105 A CN110560105 A CN 110560105A
- Authority
- CN
- China
- Prior art keywords
- composite material
- water
- znin
- ethanol
- nickel phosphide
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000004005 microsphere Substances 0.000 title claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 124
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims abstract description 18
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000002077 nanosphere Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 28
- 239000000463 material Substances 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910015335 Ni2In Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- 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
Abstract
The invention discloses a preparation method of a nickel phosphide-loaded zinc indium sulfide nano microsphere composite material and application thereof in photocatalytic hydrogen production, wherein ethanol and water are mixed, ultrasonic treatment is carried out, and Ni (oAc) is added2·4H2O and ammonia water are evenly stirred, reacted at a certain temperature, cooled, centrifugally washed and dried to obtain Ni (OH)2(ii) a With NaH2PO2Grinding Ni (OH)2Heating and preserving heat to obtain nickel phosphide; preparing mixed solution by water and ethanol, adding ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2P, ultrasonic treatment, stirring to obtain suspension, hydrothermal reaction, washing to neutrality to obtain phosphorizationThe nickel-loaded sulfur indium zinc nano microsphere composite material. The composite material is applied to photocatalytic hydrogen production. The preparation method utilizes the modified cocatalyst, effectively improves the performance of the sample, reduces the hydrogen evolution potential, accelerates the interface charge mobility, increases the photocatalytic activity and greatly improves the hydrogen production performance under visible light.
Description
Technical Field
The invention relates to nickel (Ni) phosphide2P) load zinc indium sulfide (ZnIn)2S4) The preparation method of the nano microsphere composite material is mainly used as a photocatalyst for hydrogen evolution reaction.
Background
The increasing energy crisis and the environmental pollution caused by the combustion of fossil fuels have prompted the active search for renewable and environmentally friendly alternative energy sources. Hydrogen energy can convert solar energy into storable chemical energy, thus becoming one of the important alternative energy sources. As ternary chalcogen compounds, ZnIn2S4has proper band gap and good light stability, and can be used for H2One of the most promising photocatalysts to be produced. Furthermore, ZnIn2S4The material has a unique three-dimensional peony-shaped structure, becomes a promising guest material support, is used for forming a heterostructure nano composite material with enhanced photoactivity, and draws wide attention in the field of hydrogen production by photocatalytic water decomposition. The design of the 0D/3D nanostructures with enhanced visible light absorption and efficient separation of photogenerated carriers is to enhance ZnIn2S4An efficient method of photocatalyst performance. These semiconductors having various heterostructures can enhance photocurrent and artificial photosynthesis efficiency by improving light absorption capacity and charge separation. In addition, the formation of a heterojunction may also improve the stability of the semiconductor.
First, Ni (OH) is produced by hydrothermal method2Then adding quantitative NaH2PO2Grinding, putting in a tube furnace for reaction to obtain Ni2And P. Preparing ZnIn by hydrothermal method2S4And mixing Ni2p are compounded together to obtain a 0D/3D heterostructure. As cocatalyst, Ni2P shows lower overpotential and lower charge transfer resistance in hydrogen evolution reaction, effectively improves the separation efficiency and the interface charge transfer capability of photoinduced carriers, and greatly improves ZnIn2S4Hydrogen production performance under visible light.
Disclosure of Invention
The invention aims to provide nickel phosphide-loaded zinc indium sulfide (Ni)2P/ZnIn2S4) A method for preparing a nano microsphere composite material.
The invention also aims to provide the nano microsphere composite material for producing H under photocatalysis2The use of (1).
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a nickel phosphide-loaded sulfur indium zinc nano microsphere composite material comprises the following steps:
1) Adding 0.5-1 mL of water and 0.1-0.2 g of Ni (oAc) into 10-20 mL of ethanol2·4H2Taking ethanol, water and Ni (oAc) according to the proportion of O and 1-2 mL of ammonia water respectively2·4H2O and ammonia; mixing ethanol and water, ultrasonic treating, and adding Ni (oAc)2·4H2O and ammonia water are evenly stirred, placed in an autoclave with a polytetrafluoroethylene lining, reacted for 7-9 hours at the temperature of 170-190 ℃, cooled to room temperature, centrifugally washed by water and ethanol, and dried for 6-8 hours to obtain Ni (OH)2；
2) By reacting Ni with NaH2PO2The molar ratio of (1: 9) - (11); respectively taking Ni (OH)2And NaH2PO2With NaH2PO2Grinding Ni (OH)2Obtaining a mixture, placing the mixture in a crucible with a cover, heating the mixture to 280-320 ℃ in a tube furnace, and performing N reaction2Keeping the temperature for 1.5-2.5 h under the atmosphere, cooling to room temperature, washing with water and ethanol, and drying to obtain nickel phosphide (Ni)2P）；
3) Respectively taking water and ethanol according to a volume ratio of 2-3: 1 to prepare a mixed solution; 1mmol of ZnCl is added into the mixed solution according to the volume of 1mL2·H2O, 1mmol of InCl3·H2O, 8mmol of Thioacetamide (TAA) and 0.02-0.07 mmol of Ni2Proportion of P, ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2adding P into the mixed solution, performing ultrasonic treatment, stirring for 11 ~ 13h to obtain uniform suspension, placing the suspension into a polytetrafluoroethylene ~ lined autoclave, performing hydrothermal reaction at the temperature of 170 ~ 190 ℃ for 1.5 ~ 2.5h, cooling to room temperature, washing with water and ethanol until the pH of the solution is 6 ~ 7, and performing vacuum drying at the temperature of 60 ~ 80 ℃ for 7 ~ 9h to obtain the nickel phosphide ~ loaded sulfur indium zinc (Ni ~ loaded sulfur indium zinc)2P/ZnIn2S4) A nanoparticle composite material.
Prepared Ni2P/ZnIn2S4In the nano-microsphere composite material, Ni2The mass percentage of P is 2-7%.
The other technical scheme adopted by the invention is as follows: an application of the composite material prepared by the preparation method of the nickel phosphide-loaded sulfur indium zinc nano microsphere composite material in photocatalytic hydrogen production.
The preparation method of the invention leads Ni (oAc) to be prepared by a hydrothermal method2·4H2Reaction of O with ammonia to give Ni (OH)2Then adding quantitative NaH2PO2Grinding, reacting in tubular furnace, and reacting with NaH2PO2Let Ni (OH)2Phosphating to obtain Ni2And P. Using ZnCl2·H2O、InCl3·H2O and thioacetamide are used as zinc source, indium source and sulfur source, and prepared Ni in different proportions is added2P, hydrothermal synthesis of Ni-loaded2ZnIn of P2S4A nano microsphere material. Due to ZnIn2S4The nanospheres are unique peony-like structures comprising a plurality of lamellar petals such that multiple scattering of the intermediate layer between the nanosheets is possible, thereby facilitating light harvesting. And, it may be Ni as a support on the surface2P provides more active sites. Thus, ZnIn2S4As a carrier, Ni was supported2P nano particle and Ni capture light induced electron and react with H+Reduction to H2，ZnIn2S4Trapping of photo-induced holes, separation of photo-induced electrons and photo-induced holes, Ni2P is used as a promoter to transfer more photoinduced electron and hole pairs to the surface of the catalyst with high efficiency so as to participate in oxidation-reduction reaction, thereby improving the hydrogen production efficiency.
The preparation method of the invention utilizes the method of cocatalyst modification, effectively improves the performance of the sample, reduces the hydrogen evolution potential and accelerates the interface charge mobility due to more exposed active sites, and increases the photocatalytic activity. Furthermore, use is made of Ni2P acts as a promoter, efficiently transferring more electron and hole pairs to the catalyst surface to participate in the redox reaction. The separation efficiency and the visible light absorption capacity of the photo-generated charge carriers are improved, so that the hydrogen production performance of the composite material under visible light is greatly improved.
Compared with the prior art, the preparation method is used for preparing ZnIn2S4The nano microsphere material has shorter time, is more convenient and quicker, and prepares Ni2When P is needed, nickel acetate is used as a nickel source, and Ni (OH) is synthesized firstly by a hydrothermal method2Reuse NaH2PO2Phosphating them, in contrast to the use of red or white phosphorus for preparing Ni2P, less toxicity, safer operation and simpler preparation method. Due to ZnIn2S4The nano microsphere material has multiple intermediate layers of Ni2The P nano particles can be embedded into the middle layer, so that the compounding of the two materials is tighter than that of the original method, and therefore, the hydrogen production performance of the composite material under visible light is higher.
Drawings
FIG. 1 is pure ZnIn2S4And 5% -Ni2P/ZnIn2S4Scanning electron micrograph (c).
FIG. 2 is pure ZnIn2S4And 5% -Ni2P/ZnIn2S4XRD pattern of (a).
FIG. 3 is pure ZnIn2S4、Ni2P and 5% -Ni2P/ZnIn2S4Ultraviolet diffuse reflection spectrum of (1).
FIG. 4 is pure ZnIn2S4、Ni2P and 5% -Ni2P/ZnIn2S4Electrochemical impedance diagram of (1).
FIG. 5 is pure ZnIn2S4、Ni2P, and 5% -Ni2P/ZnIn2S4Photocurrent density map of (a).
FIG. 6 is pure ZnIn2S4、Ni2P/ZnIn2S4And (3) a hydrogen production performance test chart of the composite material.
Detailed Description
The following examples illustrate Ni according to the invention2P/ZnIn2S4The preparation of the composite material and the photocatalytic hydrogen production performance are further explained.
Example 1
Preparing a mixed solution by respectively taking water and ethanol according to the volume ratio of 2: 1; 1mmol of ZnCl is added into 1mL2·H2O, 1mmol of InCl3·H2Ratio of O to 8mmol of thioacetamide, reacting ZnCl2·H2O、InCl3·H2adding O and thioacetamide into the mixed solution, carrying out ultrasonic treatment, stirring for 11 ~ 13h to obtain uniform suspension, placing the suspension into a polytetrafluoroethylene ~ lined autoclave, carrying out hydrothermal reaction for 2.5h at the temperature of 170 ℃, cooling to room temperature, washing with water and ethanol, precipitating until the pH value is neutral, and carrying out vacuum drying to obtain ZnIn2S4A composite material.
ZnIn prepared in example 12S4Application of composite material in photocatalytic water splitting for hydrogen production2The yield of (b) was 49.5umol/h/0.1 g.
Example 2
To 10mL of ethanol were added 0.5mL of water, 0.1g of Ni (oAc)2·4H2O and 1mL ammonia water, respectively taking ethanol, water and Ni (oAc)2·4H2O and ammonia; mixing ethanol and water, ultraSonicating, adding Ni (oAc)2·4H2O and ammonia water are evenly stirred, placed in an autoclave with a polytetrafluoroethylene lining, reacted for 9 hours at the temperature of 170 ℃, cooled to room temperature, centrifugally washed by water and ethanol, and dried for 6 to 8 hours to obtain Ni (OH)2(ii) a By reacting Ni with NaH2PO2At a molar ratio of 1: 9; respectively taking Ni (OH)2And NaH2PO2With NaH2PO2Grinding Ni (OH)2To give a mixture, this mixture was placed in a crucible with a lid and heated to 280 ℃ in a tube furnace at N2Keeping the temperature for 2.5h under the atmosphere, cooling to room temperature, washing with water and ethanol, and drying to obtain nickel phosphide; preparing a mixed solution by respectively taking water and ethanol according to the volume ratio of 2: 1; 1mmol of ZnCl is added into the mixed solution according to the volume of 1mL2·H2O, 1mmol of InCl3·H2O, 8mmol of thioacetamide and 0.02mmol of Ni2Proportion of P, ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2adding P into the mixed solution, carrying out ultrasonic treatment, stirring for 11 ~ 13h to obtain uniform suspension, placing the suspension into a polytetrafluoroethylene ~ lined autoclave, carrying out hydrothermal reaction for 2.5h at the temperature of 170 ℃, cooling to room temperature, washing with water and ethanol, precipitating until the pH value is neutral, and carrying out vacuum drying to obtain 2% ~ Ni2P/ZnIn2S4A nanoparticle composite material.
Example 2-Ni2P/ZnIn2S4Application of nano microsphere composite material in photocatalytic water decomposition for hydrogen production, H2The yield of (b) was 93.3umol/h/0.1 g.
Example 3
To 20 mL of ethanol were added 1mL of water, 0.2 g of Ni (oAc)2·4H2O and 2mL ammonia water, respectively taking ethanol, water and Ni (oAc)2·4H2O and ammonia; mixing ethanol and water, ultrasonic treating, and adding Ni (oAc)2·4H2O and ammonia water are evenly stirred, placed in an autoclave with a polytetrafluoroethylene lining, reacted for 7 hours at the temperature of 190 ℃, cooled to room temperature, centrifugally washed by water and ethanol, and dried for 6 to 8 hours to obtain Ni (OH)2(ii) a By reacting Ni with NaH2PO2at a molar ratio of 1: 11; respectively taking Ni (OH)2And NaH2PO2With NaH2PO2Grinding Ni (OH)2To obtain a mixture, placing the mixture in a crucible with a cover and heating to 320 ℃ in a tube furnace at N2Keeping the temperature for 1.5h under the atmosphere, cooling to room temperature, washing with water and ethanol, and drying to obtain nickel phosphide; respectively taking water and ethanol according to a volume ratio of 3: 1 to prepare a mixed solution; 1mmol of ZnCl is added into the mixed solution according to the volume of 1mL2·H2O, 1mmol of InCl3·H2O, 8mmol of Thioacetamide (TAA) and 0.05mmol of Ni2Proportion of P, ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2adding P into the mixed solution, carrying out ultrasonic treatment, stirring for 11 ~ 13h to obtain uniform suspension, placing the suspension into a polytetrafluoroethylene ~ lined autoclave, carrying out hydrothermal reaction for 1.5h at the temperature of 190 ℃, cooling to room temperature, washing with water and ethanol, precipitating until the pH value is neutral, and carrying out vacuum drying to obtain 5% ~ Ni2P/ZnIn2S4A nanoparticle composite material.
5% -Ni from example 32P/ZnIn2S4Applied to photocatalytic water splitting for producing hydrogen H2The yield of (d) was 181.2umol/h/0.1 g.
Example 4
Adding 0.75mL of water and 0.15 g of Ni (oAc) into 15 mL of ethanol2·4H2O and 1.5mL ammonia water, ethanol, water, Ni (oAc)2·4H2O and ammonia; mixing ethanol and water, ultrasonic treating, and adding Ni (oAc)2·4H2O and ammonia water are evenly stirred, placed in an autoclave with a polytetrafluoroethylene lining, reacted for 8 hours at the temperature of 180 ℃, cooled to room temperature, centrifugally washed by water and ethanol, and dried for 6 to 8 hours to obtain Ni (OH)2(ii) a By reacting Ni with NaH2PO2The molar ratio of (1: 10); respectively taking Ni (OH)2And NaH2PO2With NaH2PO2Grinding Ni (OH)2Obtaining a mixture, placing the mixture in a crucible with a cover and in a tubeHeating to 300 ℃ in a furnace at N2Keeping the temperature for 2h under the atmosphere, cooling to room temperature, washing with water and ethanol, and drying to obtain nickel phosphide; preparing a mixed solution by respectively taking water and ethanol according to a volume ratio of 2.5: 1; 1mmol of ZnCl is added into the mixed solution according to the volume of 1mL2·H2O, 1mmol of InCl3·H2O, 8mmol of Thioacetamide (TAA) and 0.07mmol of Ni2Proportion of P, ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2adding P into the mixed solution, carrying out ultrasonic treatment, stirring for 11 ~ 13h to obtain uniform suspension, placing the suspension into a polytetrafluoroethylene ~ lined autoclave, carrying out hydrothermal reaction for 1.5 ~ 2.5h at the temperature of 170 ~ 190 ℃, cooling to room temperature, washing with water and ethanol, precipitating until the pH value is neutral, and carrying out vacuum drying to obtain 7% ~ Ni2P/ZnIn2S4A nanoparticle composite material.
Example 4 preparation of 7% -Ni2P/ZnIn2S4Applied to photocatalytic water splitting for producing hydrogen H2The yield of (1) was 70.9umol/h/0.1 g.
24、Ni2P/ZnIn2S4Characterization of the composite Material
1. SEM test
FIG. 1 is the ZnIn prepared in example 12S4Materials and 5% -Ni from example 32P/ZnIn2S4Scanning electron micrographs of the composite. Wherein (a) and (b) are ZnIn2S4the scanning electron microscope images of the composite material, wherein (c) and (d) are 5% ~ Ni2P/ZnIn2S4Scanning electron micrographs of the composite. ZnIn can be seen from the two figures (a) and (b)2S4The sample is a unique lamellar peony-like spherical structure comprising many petals, which allows multiple scattering of the intermediate layer between the nanosheets, thereby facilitating light harvesting. And, it may be Ni on the surface2P quantum dots provide more active sites. As can be seen from the two graphs (c) and (d), Ni was added2P quantum dots followed by Ni2P/ZnIn2S4The composite sample no longer exhibited a unique layer shape,Proving Ni2The P quantum dots are successfully loaded on ZnIn2S4The above.
2. XRD pattern analysis
FIG. 2 shows ZnIn prepared in example 12S4Materials and 5% -Ni from example 32P/ZnIn2S4The X-ray diffraction pattern of the composite material shows that the composite material (5% -Ni) with the best hydrogen production effect2P/ZnIn2S4) With pure ZnIn2S4ZnIn prepared with the same diffraction peak2S4And ZnIn2S4All the composite samples are mixed with hexagonal ZnIn2S4the diffraction peaks of the phases (JCPDS 65 ~ 2023) are well matched, and the diffraction peaks are located at 21.6 degrees, 27.7 degrees, 30.4 degrees, 39.8 degrees, 47.2 degrees, 52.4 degrees and 55.68 degrees, and can be attributed to ZnIn of hexagonal systems of (006), (102), (104), (108), (110), (116) and (022)2S4A crystal plane of (a). And in the presence of Ni2In the case of P, ZnIn2S4Diffraction peak enhancement of the sample, ZnIn2S4The average crystallite size of the crystals increased, indicating Ni2The P quantum dots can be used as flower-shaped ZnIn2S4Nucleation sites of the crystal, thereby promoting ZnIn to some extent2S4Crystallization and growth of (2). However, Ni was not observed in the composite material2A distinct peak of P due to Ni2Low amount of P, therefore, in ZnIn2S4Sample Ni Loading2The P quantum dots have no obvious influence on the XRD pattern.
3. Ultraviolet diffuse reflectance spectrogram analysis
FIG. 3 is the ZnIn prepared in example 12S4Materials and 5% -Ni from example 32P/ZnIn2S4Ultraviolet diffuse reflection spectrogram of the composite material. As can be seen from the figure, 5% -Ni2P/ZnIn2S4Composite material and ZnIn2S4The composite material showed similar absorption edge and strong transition at about 500nm, corresponding to ZnIn with band gap of 2.49eV2S4Intrinsic bandgap absorption of semiconductors. With pure ZnIn2S4Compared with the sample, the sample is observed to be loaded with Ni in the visible light region within the range of 500-800 nm2ZnIn of P2S4The absorbance of the sample increases. Indicating the loading of Ni2P promotes the separation and transfer of electrons and holes, thereby enhancing the absorption of visible light and increasing H2Resulting in performance.
24、Ni2P/ZnIn2S4Photocatalytic performance of composite materials
1. Electrochemical Impedance Spectrogram (EIS)
Photoelectrochemical measurements were carried out in a quartz cell containing an electrolyte (pH = 7.5) containing 0.5mol Na per litre of electrolyte2SO4The platinum electrode and the saturated Ag/AgCl electrode are respectively used as a counter electrode and a reference electrode, the working electrode is FTO conductive glass with a sample coated on the surface, firstly 0.01g of the sample is taken into 1mL of absolute ethyl alcohol and mixed evenly, and naphthol solution (10 mu l) is coated on the surface area of 1cm2The sample-containing solution was dropped on the naphthol solution, dried under an infrared lamp, and irradiated from the back side with a 300W xenon lamp as a light source for light irradiation.
FIG. 4 is an electrochemical impedance spectroscopy Nyquist plot (EIS) for characterizing charge carrier transfer properties and enhanced photoelectrochemical properties, in which it can be seen that 5% -Ni prepared by example 32P/ZnIn2S4Nyquist circle radius ratio of composite pure ZnIn from example 12S4The small sample shows that the smaller the charge transfer resistance is, the more effective the separation of the photon-generated carriers and the faster interface electron transfer, and the excellent photocatalytic performance is shown.
2. Photocurrent density diagram
FIG. 5 is pure ZnIn2S4、Ni2P and 5% -Ni2P/ZnIn2S4Photocurrent density plots of the samples. Pure ZnIn can be seen2S4Photocurrent density at 1.23V vs. rhe under simulated sunlight irradiation of am1.5g was about 0.2mA cm-2，5%～Ni2P/ZnIn2S4The photocurrent density of the composite material can reach 0.4mA cm under the irradiation of AM1.5G simulated sunlight and 1.23V vs. RHE-2。5%-Ni2P/ZnIn2S4The photocurrent of the composite material was pure ZnIn2S4Photocurrent (0.2 mA cm-2) 2 times of the total weight of the powder. Shows that the composite material prepared by the preparation method improves ZnIn2S4The hydrogen production performance by photocatalytic water decomposition.
3、Ni2P/ZnIn2S4Testing of hydrogen production performance of nano microsphere material
Ni2P/ZnIn2S4The photocatalytic activity of the nano microsphere material is carried out in a specially-made closed hydrogen production reactor. In each test experiment, 0.1g of the photocatalyst powder was dispersed in 100 mL of a 0.5M aqueous solution of sodium sulfite and 0.5M sodium sulfate, the reactor was evacuated, fixed on a stirrer and irradiated under visible light with a 300W Xe lamp (a xenon lamp with a 420 nm filter (0.1M NaNO) placed thereon under stirring at a constant stirring speed2Aqueous solution)). The hydrogen production was measured once per hour, and during each test period, the hydrogen production was measured by a thermal conductivity detector (Ar carrier) using a gas chromatograph (GC 9560, china).
FIG. 6 is pure ZnIn2S4And loaded with Ni in different proportions2ZnIn of P2S4And (5) testing the hydrogen production performance of the composite sample. As can be seen from the figure, pure ZnIn2S4The hydrogen production rate under the irradiation of visible light is 49.5umol/h/0.1g, and a small amount of Ni is loaded2After P, the hydrogen production rate is improved. Wherein Ni with a molar fraction of 5% is loaded2ZnIn of P2S4The compound sample has the highest hydrogen production rate which can reach 181.5umol/h/0.1g and is pure ZnIn2S43.67 times of the sample. However, the load was 7% Ni2ZnIn of P2S4The hydrogen production rate of the sample decreased, which may be due to excessive loading, occupying ZnIn2S4Excessive active sites on the sample affect ZnIn2S4The absorption and utilization of photons, thereby leading to the reduction of the hydrogen production rate.
Claims (4)
1. A preparation method of a nickel phosphide-loaded sulfur indium zinc nano microsphere composite material is characterized by comprising the following steps:
1) adding 0.5-1 mL of water and 0.1-0.2 g of Ni (oAc) into 10-20 mL of ethanol2·4H2Taking ethanol, water and Ni (oAc) according to the proportion of O and 1-2 mL of ammonia water respectively2·4H2O and ammonia; mixing ethanol and water, ultrasonic treating, and adding Ni (oAc)2·4H2O and ammonia water are evenly stirred, the mixture is placed at the temperature of 170 ~ 190 ℃ for reaction for 7 ~ 9h, the mixture is cooled to room temperature, centrifugally washed and dried for 6 ~ 8h to obtain Ni (OH)2；
2) With NaH2PO2Grinding Ni (OH)2Obtaining a mixture, heating the mixture to 280-320 ℃ in N2Preserving heat for 1.5-2.5 h in the atmosphere, cooling to room temperature, washing, and drying to obtain nickel phosphide;
3) Preparing a mixed solution by using water and ethanol; 1mmol of ZnCl is added into the mixed solution according to the volume of 1mL2·H2O, 1mmol of InCl3·H2O, 8mmol of thioacetamide and 0.02-0.07 mmol of Ni2Proportion of P, ZnCl2·H2O、InCl3·H2O, thioacetamide and Ni2and adding P into the mixed solution, performing ultrasonic treatment, stirring for 6 ~ 8 hours to obtain uniform suspension, performing hydrothermal reaction on the suspension at the temperature of 170 ~ 190 ℃ for 1.5 ~ 2.5 hours, cooling to room temperature, washing until the pH value of the solution is 6 ~ 7, and performing vacuum drying to obtain the nickel phosphide ~ loaded sulfur indium zinc nanoparticle composite material.
2. The method for preparing the nickel phosphide-loaded zinc indium sulfide nanosphere composite material as claimed in claim 1, wherein in the step 2), during grinding, Ni and NaH are mixed2PO2The molar ratio of the components is 1: 9-11.
3. The preparation method of the nickel phosphide-loaded sulfur indium zinc nanosphere composite material as claimed in claim 1, wherein in the step 3), water and ethanol are respectively taken according to a volume ratio of 2-3: 1 to prepare a mixed solution.
4. An application of the composite material prepared by the preparation method of the nickel phosphide-loaded sulfur indium zinc nanosphere composite material as claimed in claim 1 in photocatalytic hydrogen production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825822.6A CN110560105B (en) | 2019-09-03 | 2019-09-03 | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825822.6A CN110560105B (en) | 2019-09-03 | 2019-09-03 | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110560105A true CN110560105A (en) | 2019-12-13 |
| CN110560105B CN110560105B (en) | 2022-03-01 |
Family
ID=68777305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910825822.6A Active CN110560105B (en) | 2019-09-03 | 2019-09-03 | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110560105B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822013A (en) * | 2020-07-06 | 2020-10-27 | 重庆大学 | Single-cell PN junction and accurate construction method thereof |
| CN112337491A (en) * | 2020-11-17 | 2021-02-09 | 北华大学 | Preparation method and application of nickel phosphide/indium oxide nanocomposite material applied to bifunctional photocatalysis |
| CN113751029A (en) * | 2021-10-19 | 2021-12-07 | 齐鲁工业大学 | Co9S8/ZnIn2S4Photocatalytic hydrogen production material and preparation method and application thereof |
| CN113751028A (en) * | 2021-10-12 | 2021-12-07 | 盐城工学院 | Organic-inorganic hybrid photocatalytic hydrogen evolution material and preparation method and application thereof |
| CN114950506A (en) * | 2022-06-28 | 2022-08-30 | 南京信息工程大学 | Ni 2 P/ZnIn 2 S 4 Preparation method and application of heterojunction photocatalyst |
| CN115283002A (en) * | 2022-08-25 | 2022-11-04 | 西安交通大学 | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst |
| CN115424866A (en) * | 2022-09-01 | 2022-12-02 | 杭州电子科技大学 | Preparation method of two-dimensional hexagonal-phase and rhombohedral-phase ZnIn2S4 composite homojunction photoelectrode |
| CN116078433A (en) * | 2022-12-15 | 2023-05-09 | 盐城工学院 | Ni-MOFs/Ni 2 Preparation method and application of P-edge heterostructure nanomaterial |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795661A (en) * | 2012-09-11 | 2012-11-28 | 黑龙江大学 | Method for preparing hierarchical floriform ZnIn2S4 ternary compound |
| CN103331175A (en) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | Preparation method of MoS2/ZnIn2S4 nanosheet composite material |
| CN108043436A (en) * | 2017-12-21 | 2018-05-18 | 福州大学 | The preparation method and applications of molybdenum carbide/sulfur-indium-zinc composite photo-catalyst |
| CN108479810A (en) * | 2018-03-21 | 2018-09-04 | 中国计量大学 | A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof |
| CN109821553A (en) * | 2019-01-16 | 2019-05-31 | 上海理工大学 | A kind of ZnIn for thering is adsorption photochemical catalysis to act synergistically2S4The preparation method and its effect of microballoon |
| CN110124690A (en) * | 2019-04-30 | 2019-08-16 | 江苏大学 | A kind of 1D Sb2S3Nanometer rods/3D ZnIn2S4The preparation method of composite construction |
-
2019
- 2019-09-03 CN CN201910825822.6A patent/CN110560105B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795661A (en) * | 2012-09-11 | 2012-11-28 | 黑龙江大学 | Method for preparing hierarchical floriform ZnIn2S4 ternary compound |
| CN103331175A (en) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | Preparation method of MoS2/ZnIn2S4 nanosheet composite material |
| CN108043436A (en) * | 2017-12-21 | 2018-05-18 | 福州大学 | The preparation method and applications of molybdenum carbide/sulfur-indium-zinc composite photo-catalyst |
| CN108479810A (en) * | 2018-03-21 | 2018-09-04 | 中国计量大学 | A kind of WS2/ZnIn2S4Composite visible light catalyst and preparation method thereof |
| CN109821553A (en) * | 2019-01-16 | 2019-05-31 | 上海理工大学 | A kind of ZnIn for thering is adsorption photochemical catalysis to act synergistically2S4The preparation method and its effect of microballoon |
| CN110124690A (en) * | 2019-04-30 | 2019-08-16 | 江苏大学 | A kind of 1D Sb2S3Nanometer rods/3D ZnIn2S4The preparation method of composite construction |
Non-Patent Citations (4)
| Title |
|---|
| DEQIAN ZENG ET AL.: ""Hierarchical flower-like ZnIn2S4 anchored with well-dispersed Ni12P5 nanoparticles for high-quantum-yield photocatalytic H2 evolution under visible light"", 《CATALYSIS SCIENCE &TECHNOLOGY》 * |
| LI-LI CHU: ""Synthesis of Ni2P/Zn3In2S6 hierarchical heterostructure for improving photocatalytic H2 evolution"", 《CATALYSIS COMMUNICATIONS》 * |
| SHIXIANG DUAN ET AL.: ""Efficient photocatalytic hydrogen production from formic acid on inexpensive and stable phosphide/Zn3In2S6 composite photocatalysts under mild conditions"", 《INTERNATIONAL JOURNAL O F HYDROGEN ENERGY》 * |
| 李旭力: ""非贵金属磷化物对三元含铟硫化物的修饰及其光催化产氢性能研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822013A (en) * | 2020-07-06 | 2020-10-27 | 重庆大学 | Single-cell PN junction and accurate construction method thereof |
| CN112337491B (en) * | 2020-11-17 | 2023-04-07 | 北华大学 | Preparation method and application of nickel phosphide/indium oxide nanocomposite material applied to bifunctional photocatalysis |
| CN112337491A (en) * | 2020-11-17 | 2021-02-09 | 北华大学 | Preparation method and application of nickel phosphide/indium oxide nanocomposite material applied to bifunctional photocatalysis |
| CN113751028A (en) * | 2021-10-12 | 2021-12-07 | 盐城工学院 | Organic-inorganic hybrid photocatalytic hydrogen evolution material and preparation method and application thereof |
| CN113751028B (en) * | 2021-10-12 | 2023-11-10 | 盐城工学院 | Organic-inorganic hybrid photocatalytic hydrogen evolution material and preparation method and application thereof |
| CN113751029A (en) * | 2021-10-19 | 2021-12-07 | 齐鲁工业大学 | Co9S8/ZnIn2S4Photocatalytic hydrogen production material and preparation method and application thereof |
| CN113751029B (en) * | 2021-10-19 | 2023-10-17 | 齐鲁工业大学 | Co (cobalt) 9 S 8 /ZnIn 2 S 4 Photocatalytic hydrogen production material and preparation method and application thereof |
| CN114950506B (en) * | 2022-06-28 | 2023-09-19 | 南京信息工程大学 | Ni (nickel) 2 P/ZnIn 2 S 4 Heterojunction photocatalyst preparation method and application thereof |
| CN114950506A (en) * | 2022-06-28 | 2022-08-30 | 南京信息工程大学 | Ni 2 P/ZnIn 2 S 4 Preparation method and application of heterojunction photocatalyst |
| CN115283002A (en) * | 2022-08-25 | 2022-11-04 | 西安交通大学 | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst |
| CN115424866A (en) * | 2022-09-01 | 2022-12-02 | 杭州电子科技大学 | Preparation method of two-dimensional hexagonal-phase and rhombohedral-phase ZnIn2S4 composite homojunction photoelectrode |
| CN115424866B (en) * | 2022-09-01 | 2024-04-05 | 杭州电子科技大学 | Preparation method of two-dimensional hexagonal phase and rhombic phase ZnIn2S4 composite homojunction photoelectrode |
| CN116078433A (en) * | 2022-12-15 | 2023-05-09 | 盐城工学院 | Ni-MOFs/Ni 2 Preparation method and application of P-edge heterostructure nanomaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110560105B (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110560105B (en) | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production | |
| Ma et al. | Knack behind the high performance CdS/ZnS-NiS nanocomposites: Optimizing synergistic effect between cocatalyst and heterostructure for boosting hydrogen evolution | |
| Zhang et al. | Sandwich-like P-doped h-BN/ZnIn2S4 nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H2 and H2O2 evolution | |
| Wang et al. | MoS 2/CQDs obtained by photoreduction for assembly of a ternary MoS 2/CQDs/ZnIn 2 S 4 nanocomposite for efficient photocatalytic hydrogen evolution under visible light | |
| Yang et al. | Porous Sn3O4 nanosheets on PPy hollow rod with photo-induced electrons oriented migration for enhanced visible-light hydrogen production | |
| Deng et al. | Compositional regulation and modification of the host CdS for efficient photocatalytic hydrogen production: case study on MoS2 decorated Co0. 2Cd0. 8S nanorods | |
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN114588888B (en) | Photocatalyst, and preparation method and application thereof | |
| CN112427045A (en) | CdS/g-C synthesized by hydrothermal method and having Z-shaped heterojunction3N4Preparation method of composite photocatalyst material | |
| CN110227500A (en) | A kind of Cd1-xZnxS-Ni/MoS2Composite photo-catalyst and preparation method thereof, application | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| Li et al. | Effect of visible light irradiation on hydrogen production by CoNi2S4/CdWO4 controllable flower spherical photocatalyst | |
| CN109550493A (en) | The preparation of carbon quantum dot carried titanium dioxide nanocomposite and its application of photocatalytic reduction of carbon oxide | |
| Zhang et al. | MOF templated to construct hierarchical ZnIn2S4-In2S3 hollow nanotube for enhancing photocatalytic performance | |
| Chen et al. | Up-conversion fluorescent carbon quantum dots decorated covalent triazine frameworks as efficient metal-free photocatalyst for hydrogen evolution | |
| Xue et al. | C3N4 nanosheets loaded with the CuWO4 activated NiS co-catalyst: A stable noble metal-free photocatalyst with dramatic photocatalytic activity for H2 generation and high salinity tolerant | |
| CN115069262A (en) | Oxygen vacancy modified MoO 3-x /Fe-W 18 O 49 Photocatalyst, preparation thereof and application thereof in nitrogen fixation | |
| CN112023947A (en) | Composite material and preparation method and application thereof | |
| CN110756199A (en) | Preparation method and application of composite photocatalyst based on nickel sulfide quantum dots | |
| Wang et al. | CdS/ZnIn 2 S 4 type II heterojunctions improve photocatalytic hydrogen production: faster electron–hole separation and wider visible light utilization | |
| CN112588324B (en) | Method for preparing composite photocatalyst CdS/ZIF-8 by one-pot method and application thereof | |
| CN109046391A (en) | A kind of composite material and preparation method and the application in visible photocatalysis aquatic products hydrogen | |
| CN108311163A (en) | A kind of bismuth oxybromide composite photo-catalyst and preparation method thereof for hydrogen manufacturing | |
| He et al. | In situ grown CdS on 2D Cd-based porphyrin MOFs enhances the significant separation and transfer of charge carriers with an appropriate heterojunction during photocatalytic hydrogen evolution | |
| Liu et al. | An experimental study on the Co–C 3 N 4/BiPO 4 composite for efficient photocatalytic water splitting |
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 |