CN106549068B - A kind of Ag@Ag2S/TiO2The synthetic method of nanometer stick array - Google Patents

A kind of Ag@Ag2S/TiO2The synthetic method of nanometer stick array Download PDF

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CN106549068B
CN106549068B CN201610833719.2A CN201610833719A CN106549068B CN 106549068 B CN106549068 B CN 106549068B CN 201610833719 A CN201610833719 A CN 201610833719A CN 106549068 B CN106549068 B CN 106549068B
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tio
stick array
nanometer stick
solution
array
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CN106549068A (en
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徐芳
陈会敏
梅晶晶
蒋凯
武大鹏
高志永
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Henan Normal University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/0296Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/0304Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
    • H01L31/03042Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds characterised by the doping material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0324Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te

Abstract

The invention discloses a kind of Ag@Ag2S/TiO2The synthetic method of nanometer stick array, concretely comprises the following steps:(1)TiO is prepared on FTO electro-conductive glass2Nanometer stick array,(2)By TiO2Nanometer stick array immerses AgNO3Precursor solution and with ultraviolet light prepare Ag modification TiO2Nanometer stick array;(3)The TiO that Ag is modified2Nanometer stick array is immersed dissolved with Na2In more sulphur solution of S and S, react and Ag@Ag are made2S/TiO2Nanometer stick array.The present invention utilizes Ag and Ag2The synergistic effect of S can improve absorption of the material to visible ray, transmission, the separative efficiency of photogenerated charge are improved, obtains the light anode material with high light solution water efficiency, and the synthetic method craft is simple, the implementing process of electrode is simplified, is conducive to mass produce.

Description

A kind of Ag@Ag2S/TiO2The synthetic method of nanometer stick array
Technical field
The invention belongs to the synthesis technical field of composite nano materials, and in particular to a kind of Ag@Ag2S/TiO2Nanometer rods battle array The synthetic method of row.
Background technology
With the fast development of science and technology and the modern industry, fossil energy is exhausted and environmental pollution has become influence society Understand the principal element of sustainable development, therefore the exploitation and utilization of clean energy resource are extremely urgent.Solar energy is a huge energy Source treasure-house, is widely used in the hot fields such as solar cell power generation, photocatalysis and photoelectrocatalysis hydrogen production by water decomposition.Day in 1972 This scholar Fujishima and Honda use monocrystalline n-TiO2Water is decomposed as light anode, has opened TiO2As photoelectrochemical credit Solve the prelude of water light anode.
TiO2Band gap be 3.4eV, the ultraviolet light for occupying sunlight 5% can only be absorbed, seriously affected TiO2To sunlight Efficiently use.In order to improve TiO2To the capture ability of incident sunlight, generally use doping, narrow gap semiconductor sensitization, The methods of heterogeneous section and plasma metal-modified, improves TiO2Absorption to visible ray or near infrared light.Publication No. The patent of CN103151175A discloses a kind of CdS quantum dot sensitization TiO2The preparation method of branched nanostructured, this method CdS/TiO is successfully prepared using continuous chemical water-bath sedimentation2Structure, CdS is narrow gap semiconductor, can improve light For anode in the absorption of visible region, but Cd element photoetch situations are serious, and can produce pollution to environment.
Ag is a kind of widely applied plasma resonance metal, and the surface plasma resonance effect of Ag, which utilizes, improves TiO2It is right The absorption of visible ray, improves transmission and the separative efficiency of photogenerated charge.Ag2The band gap of S is 0.92eV, can absorb solar spectrum In near infrared light, therefore, design synthesis Ag@Ag2S/TiO2Light anode can make TiO2Light anode is for incident sunlight Response range is widened near infrared region.
The content of the invention
The technical problem to be solved by the present invention is to provide a kind of easy Ag being combined using photo-reduction and ion exchange Ag2S/TiO2The synthetic method of nanometer stick array.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of Ag@Ag2S/TiO2Nanometer stick array Synthetic method, it is characterised in that concretely comprise the following steps:
(1)Added in 24mL deionized waters, the concentrated hydrochloric acid and 2mL acetic acid mixed solutions that 22mL mass fractions are 37% 0.8mL butyl titanates, stir to solution and clarify, be then transferred to solution and be placed with the hydrothermal reaction kettle of FTO electro-conductive glass, In 150 DEG C of hydro-thermal reaction 20h, cooled to room temperature, takes out sample clean and totally dries and obtained in 450 DEG C of annealing 30min afterwards To the TiO that length is 3-4 μm2Nanometer stick array;
(2)By step(1)Obtained TiO2Nanometer stick array is immersed dissolved with AgNO3With the alcohol-water of polyvinylpyrrolidone In solution, 10-50min is irradiated under ultraviolet light, and sample is then taken out into cleaning and naturally dry obtains the TiO of Ag modifications2Receive Rice rod array;
(3)By step(2)The TiO of obtained Ag modifications2Nanometer stick array is immersed dissolved with Na230- is reacted in the solution of S and S 90min, then takes out cleaning by sample and naturally dry obtains Ag@Ag2S/TiO2Nanometer stick array.
Further preferably, step(2)Described in dissolved with AgNO3In the ethanol-water solution of polyvinylpyrrolidone AgNO3Molar concentration be 0.5-2mmol/L, the mass concentration of polyvinylpyrrolidone is the volume ratio of 1g/L, water and ethanol For 1:1.
Further preferably, step(3)Described in dissolved with Na2Na in the solution of S and S2The total mol concentration of S and S is 1mol/L。
The present invention utilizes Ag and Ag2The synergistic effect of S can improve absorption of the material to visible ray, improve photogenerated charge Transmission, separative efficiency, obtain the light anode material with high light solution water efficiency, and the synthetic method craft is simple, letter The implementing process of electrode is changed, has been conducive to mass produce.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair Bright scope.
Embodiment 1
(1)Added in 24mL deionized waters, the concentrated hydrochloric acid and 2mL acetic acid mixed solutions that 22mL mass fractions are 37% 0.8mL butyl titanates, stir to solution and clarify, be then transferred to solution and be placed with the hydrothermal reaction kettle of FTO electro-conductive glass, In 150 DEG C of hydro-thermal reaction 20h, cooled to room temperature, takes out sample clean and totally dries and obtained in 450 DEG C of annealing 30min afterwards To the TiO that length is 3-4 μm2Nanometer stick array;
(2)By step(1)Obtained TiO2Nanometer stick array immerses 100mL dissolved with AgNO3And polyvinylpyrrolidone (PVP)Ethanol and aqueous solution in, wherein AgNO3Molar concentration be 2mmol/L, the mass concentration of PVP is 1g/L, water and second The volume ratio of alcohol is 1:1,10min is irradiated under ultraviolet light, and sample is then taken out into cleaning and naturally dry obtains Ag modifications TiO2Nanometer stick array;
(3)By step(2)The TiO of obtained Ag modifications2Nanometer stick array is immersed dissolved with Na2The total mol concentration of S and S is 60min is reacted in more sulphur solution of 1mol/L, sample is then taken out into cleaning and naturally dry obtains Ag@Ag2S/TiO2Nanometer rods Array.
Embodiment 2
(1)Added in 24mL deionized waters, the concentrated hydrochloric acid and 2mL acetic acid mixed solutions that 22mL mass fractions are 37% 0.8mL butyl titanates, stir to solution and clarify, be then transferred to solution and be placed with the hydrothermal reaction kettle of FTO electro-conductive glass, In 150 DEG C of hydro-thermal reaction 20h, cooled to room temperature, takes out sample clean and totally dries and obtained in 450 DEG C of annealing 30min afterwards To the TiO that length is 3-4 μm2Nanometer stick array;
(2)By step(1)Obtained TiO2Nanometer stick array immerses 100mL dissolved with AgNO3With the ethanol and aqueous solution of PVP In, wherein AgNO3Molar concentration be 1mmol/L, the mass concentration of PVP is 1g/L, and the volume ratio of water and ethanol is 1:1, 30min is irradiated under ultraviolet light, sample is then taken out into cleaning and naturally dry obtains the TiO of Ag modifications2Nanometer stick array;
(3)By step(2)The TiO of obtained Ag modifications2Nanometer stick array is immersed dissolved with Na2The total mol concentration of S and S is 30min is reacted in more sulphur solution of 1mol/L, sample is then taken out into cleaning and naturally dry obtains Ag@Ag2S/TiO2Nanometer rods Array.
Embodiment 3
(1)Added in 24mL deionized waters, the concentrated hydrochloric acid and 2mL acetic acid mixed solutions that 22mL mass fractions are 37% 0.8mL butyl titanates, stir to solution and clarify, be then transferred to solution and be placed with the hydrothermal reaction kettle of FTO electro-conductive glass, In 150 DEG C of hydro-thermal reaction 20h, cooled to room temperature, takes out sample clean and totally dries and obtained in 450 DEG C of annealing 30min afterwards To the TiO that length is 3-4 μm2Nanometer stick array;
(2)By step(1)Obtained TiO2Nanometer stick array immerses 100mL dissolved with AgNO3With the ethanol and aqueous solution of PVP In, wherein AgNO3Molar concentration be 0.5mmol/L, the mass concentration of PVP is 1g/L, and the volume ratio of water and ethanol is 1:1, 50min is irradiated under ultraviolet light, and sample is then taken out into cleaning and naturally dry obtains the TiO of Ag modifications2Nanometer stick array;
(3)By step(2)The TiO of obtained Ag modifications2Nanometer stick array is immersed dissolved with Na2The total mol concentration of S and S is 90min is reacted in more sulphur solution of 1mol/L, sample is then taken out into cleaning and naturally dry obtains Ag@Ag2S/TiO2Nanometer rods Array.
Basic principle, main features and advantages embodiment above describes the present invention, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the original of the present invention Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (1)

  1. A kind of 1. Ag@Ag2S/TiO2The synthetic method of nanometer stick array, it is characterised in that concretely comprise the following steps:
    (1)0.8mL metatitanic acids are added in 24mL deionized waters, the concentrated hydrochloric acid of 22mL mass fractions 37% and 2mL acetic acid mixed solutions Four butyl esters, stir to solution and clarify, be then transferred to solution and be placed with the hydrothermal reaction kettle of FTO electro-conductive glass, in 150 DEG C of water Thermal response 20h, cooled to room temperature, it is 3- to take out sample clean and totally dry afterwards and obtain length in 450 DEG C of annealing 30min 4 μm of TiO2Nanometer stick array;
    (2)By step(1)Obtained TiO2Nanometer stick array is immersed dissolved with AgNO3With the ethanol-water solution of polyvinylpyrrolidone In, 10-50min is irradiated under ultraviolet light, and sample is then taken out into cleaning and naturally dry obtains the TiO of Ag modifications2Nanometer rods Array, it is described dissolved with AgNO3With AgNO in the ethanol-water solution of polyvinylpyrrolidone3Molar concentration be 0.5-2mmol/L, The mass concentration of polyvinylpyrrolidone is 1g/L, and the volume ratio of water and ethanol is 1:1;
    (3)By step(2)The TiO of obtained Ag modifications2Nanometer stick array is immersed dissolved with Na230- is reacted in the solution of S and S 90min, then takes out cleaning by sample and naturally dry obtains Ag@Ag2S/TiO2Nanometer stick array, it is described dissolved with Na2S and S Solution in Na2The total mol concentration of S and S is 1mol/L.
CN201610833719.2A 2016-09-20 2016-09-20 A kind of Ag@Ag2S/TiO2The synthetic method of nanometer stick array Expired - Fee Related CN106549068B (en)

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CN108311131A (en) * 2017-12-21 2018-07-24 安徽理工大学 A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material and preparation method
CN108751738A (en) * 2018-06-01 2018-11-06 合肥学院 A kind of Bi2S3/TiO2Composite material nanometer stick array and preparation method
CN110487769A (en) * 2019-06-28 2019-11-22 江汉大学 A kind of preparation method and applications of titanic oxide nanorod array/argentum nano composite material
CN110344096B (en) * 2019-07-26 2021-09-10 中国科学院海洋研究所 AgSbS2Sensitized TiO2Composite membrane material and preparation and application thereof
CN110940718B (en) * 2019-12-10 2022-04-01 集美大学 Near-infrared photoelectric Ag2Preparation and test method of S @ Au cubic material

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN103205760A (en) * 2013-04-27 2013-07-17 厦门大学 Preparation method of Ag2S/TiO2 composite film photo-anode for photoproduction cathode protection
CN105621349A (en) * 2016-01-05 2016-06-01 河南师范大学 Method for synthesizing Au and Ag co-modified TiO2 nanorod array by use of photo-reduction method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205760A (en) * 2013-04-27 2013-07-17 厦门大学 Preparation method of Ag2S/TiO2 composite film photo-anode for photoproduction cathode protection
CN105621349A (en) * 2016-01-05 2016-06-01 河南师范大学 Method for synthesizing Au and Ag co-modified TiO2 nanorod array by use of photo-reduction method

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