WO2022198766A1 - 原位合成的全固态z型异质结构光催化剂及其制备方法、光电催化合成h 2o 2中的应用 - Google Patents

原位合成的全固态z型异质结构光催化剂及其制备方法、光电催化合成h 2o 2中的应用 Download PDF

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WO2022198766A1
WO2022198766A1 PCT/CN2021/093269 CN2021093269W WO2022198766A1 WO 2022198766 A1 WO2022198766 A1 WO 2022198766A1 CN 2021093269 W CN2021093269 W CN 2021093269W WO 2022198766 A1 WO2022198766 A1 WO 2022198766A1
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tio
mose
annealing treatment
present
preparation
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French (fr)
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张旭东
林仕伟
陈汉德
符坚
周义龙
陈宝
林正玺
王玲转
林慧媛
符智豪
黄修彩
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海南聚能科技创新研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • the invention belongs to the technical field of photoelectric catalytic synthesis of H 2 O 2 , and relates to a 1T/2H-MoSe 2 @TiO 2 nanocomposite material, a preparation method and application thereof, and in particular to an in-situ synthesized all-solid Z-type heterostructure Photocatalyst and preparation method thereof, and application in photocatalytic production of H2O2 .
  • the industrial synthesis methods of hydrogen peroxide mainly include the anthraquinone method and the direct synthesis of hydrogen (H 2 ) and oxygen (O 2 ), but the anthraquinone method involves different hydrogenation and oxidation reactions, which consume a large amount of The organic solvent and energy, and the direct synthesis of H2 and O2 is prone to explosion. Therefore, there is a constant need in the industry to find an efficient method for synthesizing H2O2 that is safe, environmentally friendly, and energy - saving. In recent years, many researchers have proposed many feasible methods to produce H2O2.
  • Photocatalytic technology has become one of the most promising methods for the production of H2O2 due to its advantages of safety, environmental protection and energy saving, which mainly relies on the production of H2O on semiconductor materials using water ( H2O ) and O2 as raw materials 2 , because the electrons generated by the semiconductor material under light irradiation conditions can reduce O 2 to form H 2 O 2 .
  • This process can be divided into a continuous two-step one-step electron oxygen reduction, as shown in reaction formula (1) and reaction (2), or a direct two-electron reduction of O2 , as shown in reaction formula (3).
  • photoelectrochemistry can also be used as an efficient method to reduce O2 to produce H2O2.
  • the semiconductor material can generate electron-hole pairs under light excitation, and then the conduction band electrons can transfer the electrons to the counter electrode to reduce O 2 to generate H 2 O 2 by applying a bias voltage, so the electrons can be separated more effectively - Hole pair.
  • TiO2 -based photocatalysts have been widely studied due to their low toxicity, high conduction band gap, and high chemical stability.
  • the low yield of TiO photocatalytic preparation of H 2 O 2 can be attributed to the following three main reasons: 1) the absorption spectrum is limited to the ultraviolet (UV) region due to the inherent wide band gap (about 3.2 eV); 2) The separation ability of photogenerated electrons and holes is poor, and electrons and holes are easily recombined in vivo; 3) H 2 O 2 adsorbed on the surface of TiO 2 is decomposed by forming peroxide (Ti-OOH) under illumination.
  • UV ultraviolet
  • Ti-OOH peroxide
  • the technical problem to be solved by the present invention is to provide a 1T/2H-MoSe 2 @TiO 2 nanocomposite material and its preparation method and application, especially an in-situ synthesized all-solid-state Z-type heterostructured light
  • the catalyst, the 1T/2H-MoSe 2 @TiO 2 nanocomposite material prepared by the present invention is a system in which semiconductor TiO 2 and MoSe 2 are heterogeneously combined, and contains a 2H semiconductor phase and a 1T metal phase, and is an all-solid-state Z-type light
  • the catalyst can improve the photocatalytic performance of the photocatalyst and increase the output of H 2 O 2 .
  • the preparation method is simple, the conditions are mild, and the process is controllable, which is beneficial to the realization of industrialization and has broad practical prospects.
  • the invention provides a 1T/2H-MoSe 2 @TiO 2 nano-composite material, which comprises TiO 2 nano-rods and MoSe 2 nano-particles compounded on the TiO 2 nano-rods;
  • the MoSe 2 nanoparticles include mixed-phase MoSe 2 nanoparticles
  • the mixed phase includes a 1T metal phase and a 2H semiconductor phase.
  • the length of the TiO 2 nanorods is 1.8-2 ⁇ m;
  • the diameter of the TiO 2 nanorods is 150-250 nm
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material includes 1T/2H-MoSe 2 @TiO 2 nanocomposite material for photoelectric catalysis;
  • the photoelectric catalysis includes photoelectric catalytic synthesis of H 2 O 2 .
  • the particle size of the MoSe 2 nanoparticles is 15-25 nm;
  • the compounding includes cladding
  • the TiO 2 includes rutile phase TiO 2 ;
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material is an all-solid-state Z-type heterostructure photocatalyst
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite is obtained from raw materials by hydrothermal method and element doping.
  • the invention provides a preparation method of 1T/2H-MoSe 2 @TiO 2 nanocomposite material, comprising the following steps:
  • the conductive substrate is placed in a TiO 2 precursor solution for hydrothermal reaction, and then annealed to obtain TiO 2 nanorods;
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite is obtained after the intermediate product obtained in the above steps is continued to be annealed.
  • the manner in which the conductive substrate is placed includes punching down the conductive surface of the conductive substrate and leaning against the inner wall of the reaction vessel;
  • the TiO 2 precursor solution includes a titanium source, an acid and water;
  • the titanium source includes tetrabutyl titanate
  • the acid includes hydrochloric acid
  • the volume ratio of the titanium source, acid and water is 0.4:(5-15):(5-15).
  • the temperature of the hydrothermal reaction is 150-180°C;
  • the time of the hydrothermal reaction is 15 to 24 hours;
  • the annealing treatment includes annealing treatment in an air atmosphere
  • the time of the annealing treatment is 2 to 3 hours;
  • the temperature of the annealing treatment is 400-500°C.
  • the selenium powder solution includes a hydrazine hydrate solution of selenium powder
  • the mass-volume ratio of the selenium powder and hydrazine hydrate is (0.025-0.034) g: 1 mL;
  • the molybdate solution includes an aqueous sodium molybdate dihydrate solution
  • the mass-volume ratio of the sodium molybdate dihydrate and water is (0.009-0.012) g: 1 mL;
  • the mass ratio of the selenium powder and the molybdate is (0.65-0.7):1.
  • the temperature of the second hydrothermal reaction is 170-190°C;
  • the time of the hydrothermal reaction again is 0.5 to 2 hours;
  • the time for the re-annealing treatment is 2 to 3 hours;
  • the temperature of the re-annealing treatment is 400-450°C;
  • the re-annealing treatment includes annealing treatment in an argon atmosphere
  • the TiO 2 nanorods have an array structure.
  • the time for the continued annealing treatment is 0.5 to 2 hours;
  • the temperature of the continuous annealing treatment is 400-450°C;
  • the heating rate of the continuous annealing treatment is 5-10°C/min;
  • the flow rate of the ammonia-containing atmosphere is 50-150 mL/min;
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite has an array structure.
  • the present invention also provides the 1T/2H-MoSe 2 @TiO 2 nanocomposite material described in any one of the above technical solutions or the 1T/2H-MoSe 2 @TiO 2 prepared by the preparation method described in any one of the above technical solutions Application of nanocomposites in the field of photocatalysts.
  • the present invention provides a 1T/2H-MoSe 2 @TiO 2 nanocomposite material, comprising TiO 2 nanorods and MoSe 2 nanoparticles compounded on the TiO 2 nanorods; the MoSe 2 nanoparticles include mixed phase MoSe 2 nanometers Particles; the mixed phase comprises a 1T metallic phase and a 2H semiconducting phase.
  • the present invention is based on the existing semiconductor catalysts.
  • the photocatalyst of TiO 2 has the characteristics of low toxicity, high conduction band gap and high chemical stability, etc.
  • the method for improving the photocatalytic performance of TiO 2 is mainly to construct a type II heterojunction, but this heterostructure is not conducive to the formation of active radicals, so it is not conducive to the preparation of H 2 O 2 (over hydrogen oxide).
  • the invention creatively obtains 1T/2H-MoSe 2 @TiO 2 nanocomposite material, the composite material has specific morphology, structure and Z-type heterostructure, which is a combination of semiconductor TiO 2 and 2H-MoSe 2 heterogeneity , the obtained semiconducting TiO 2 and MoSe 2 hetero-combined system.
  • the nanocomposite material provided by the invention contains 2H semiconductor phase and 1T metal phase, and is an all-solid Z-type composite material.
  • the composite material provided by the invention is used as a photocatalyst, a small part of 2H-MoSe 2 is converted into 1T-MoSe 2 , the synthesis of 1T phase acts as a bridge for electron transfer, and further promotes the separation of electron-hole pairs, thus the constructed photoelectric catalytic system , can greatly improve the photoelectric catalytic performance, and then increase the output of H 2 O 2 , which is more conducive to the production of H 2 O 2 .
  • the preparation method provided by the present invention is simple, the conditions are mild, and the process is controllable, which is favorable for industrialization and has broad practical prospects.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material provided by the present invention is used as an all-solid Z-type composite system photocatalyst.
  • the all-solid Z-type system photocatalyst is prepared, which is used for photoelectric catalysis to prepare H 2 O 2 .
  • Fig. 1 is a schematic diagram of the process flow for preparing 1T/2H-MoSe 2 @TiO 2 according to the present invention
  • Figure 2 is a scanning electron microscope image of TiO 2 , 2H-MoSe 2 @TiO 2 and 1T/2H-MoSe 2 @TiO 2 prepared by the present invention
  • Fig. 3 is the TEM image, HRTEM image and element Mapping image of 1T metal phase and 2H semiconductor phase coexisting in MoSe 2 nanoparticles and successfully modified on TiO 2 prepared in the embodiment of the present invention
  • Figure 4 is a graph of transient photocurrent curves of 2H-MoSe 2 @TiO 2 prepared with different hydrothermal times in the embodiment of the present invention
  • FIG. 6 is a comparison diagram of the yield of 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention and other catalysts or H 2 O 2 without catalyst;
  • Figure 7 is a graph showing the comparison of the photoelectric catalytic degradation of H 2 O 2 between 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention and other catalysts or without catalysts;
  • FIG. 8 is a cycle stability test chart of H 2 O 2 prepared from 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention.
  • the raw material used in the present invention is not particularly limited in its purity, and in the present invention, it is preferably analytical purity or conventional purity in the field of photocatalyst preparation.
  • the invention provides a 1T/2H-MoSe 2 @TiO 2 nano-composite material, which comprises TiO 2 nano-rods and MoSe 2 nano-particles compounded on the TiO 2 nano-rods;
  • the MoSe 2 nanoparticles include mixed-phase MoSe 2 nanoparticles
  • the mixed phase includes a 1T metal phase and a 2H semiconductor phase.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material of the present invention includes TiO 2 nanorods.
  • the length of the TiO 2 nanorods is preferably 1.8-2 ⁇ m, more preferably 1.82-1.98 ⁇ m, more preferably 1.85-1.95 ⁇ m, more preferably 1.87-1.93 ⁇ m.
  • the diameter of the TiO 2 nanorods is preferably 150-250 nm, more preferably 170-230 nm, and more preferably 190-210 nm.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material according to the present invention also includes MoSe 2 nanoparticles compounded on the TiO 2 nanorods.
  • the MoSe 2 nanoparticles include mixed-phase MoSe 2 nanoparticles.
  • the MoSe 2 nanoparticles are a mixed phase, and the mixed phase includes a 1T metal phase and a 2H semiconductor phase.
  • the particle size of the MoSe 2 nanoparticles is preferably 15-25 nm, more preferably 17-23 nm, and more preferably 19-21 nm.
  • the compounding may specifically be cladding.
  • the TiO 2 preferably includes rutile phase TiO 2 .
  • the TiO 2 nanorods have an array structure. Furthermore, the 1T/2H-MoSe 2 @TiO 2 nanocomposite also has an array structure.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite preferably includes 1T/2H-MoSe 2 @TiO 2 nanocomposite for photoelectric catalysis.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material is preferably an all-solid-state Z-type heterostructure photocatalyst.
  • the photoelectric catalysis preferably includes photoelectric catalytic synthesis of H 2 O 2 .
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material is obtained from raw materials by hydrothermal method and element doping.
  • the invention provides a preparation method of 1T/2H-MoSe 2 @TiO 2 nanocomposite material, comprising the following steps:
  • the conductive substrate is placed in a TiO 2 precursor solution for hydrothermal reaction, and then annealed to obtain TiO 2 nanorods;
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite is obtained after the intermediate product obtained in the above steps is continued to be annealed.
  • the conductive substrate is firstly placed in a TiO 2 precursor solution to perform a hydrothermal reaction, and then annealed to obtain a TiO 2 nanorod.
  • the conductive substrate preferably includes conductive glass (FTO).
  • FTO conductive glass
  • the manner in which the conductive substrate is placed preferably includes the conductive surface of the conductive substrate being flushed down and leaning against the inner wall of the reaction vessel.
  • the TiO 2 precursor solution preferably includes a titanium source, an acid and water.
  • the titanium source preferably includes tetrabutyl titanate.
  • the acid preferably includes hydrochloric acid.
  • the volume ratio of the titanium source and the acid is preferably 0.4:(5-15), more preferably 0.4:(7-13), and more preferably 0.4:(9-11).
  • the volume ratio of the titanium source and water is preferably 0.4:(5-15), more preferably 0.4:(7-13), and more preferably 0.4:(9-11).
  • the temperature of the hydrothermal reaction is preferably 150 to 180°C, more preferably 155 to 175°C, and more preferably 160 to 170°C.
  • the time of the hydrothermal reaction is preferably 15 to 24 hours, more preferably 17 to 22 hours, and more preferably 19 to 20 hours.
  • the annealing treatment preferably includes an annealing treatment in an air atmosphere.
  • the time of the annealing treatment is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, and more preferably 2.4 to 2.6 hours.
  • the temperature of the annealing treatment is preferably 400 to 500°C, more preferably 420 to 480°C, and more preferably 440 to 460°C.
  • the selenium powder solution and the molybdate solution are mixed to obtain a precursor solution, and the TiO2 nanorods obtained in the above steps are placed in the precursor solution for hydrothermal reaction again, and after annealing treatment again, an intermediate product 2H- MoSe 2 @TiO 2 .
  • the selenium powder solution preferably includes a hydrazine hydrate solution of selenium powder.
  • the mass-volume ratio of the selenium powder and hydrazine hydrate is preferably (0.025-0.034) g: 1 mL, more preferably (0.027-0.032) g: 1 mL, more preferably (0.029-0.030) g: 1 mL .
  • the molybdate solution preferably includes an aqueous solution of sodium molybdate dihydrate.
  • the mass-volume ratio of the sodium molybdate dihydrate and water is preferably (0.009-0.012) g: 1 mL, more preferably (0.009-0.011) g: 1 mL, more preferably (0.01-0.012) g : 1mL.
  • the mass ratio of the selenium powder and the molybdate is preferably (0.65-0.7):1, more preferably (0.66-0.69):1, more preferably (0.67-0.68):1.
  • the temperature of the second hydrothermal reaction is preferably 170-190°C, more preferably 172-188°C, more preferably 175-185°C, and more preferably 177-183°C.
  • the time for the second hydrothermal reaction is preferably 0.5 to 2 hours, more preferably 0.7 to 1.8 hours, and more preferably 1.0 to 1.5 hours.
  • the time for the re-annealing treatment is preferably 2 to 3 hours, more preferably 2.2 to 2.8 hours, and more preferably 2.4 to 2.6 hours.
  • the temperature of the re-annealing treatment is preferably 400 to 450°C, more preferably 410 to 440°C, and more preferably 420 to 430°C.
  • the annealing treatment preferably includes an annealing treatment in an argon atmosphere.
  • 1T/2H-MoSe 2 @TiO 2 nanocomposite is obtained after the intermediate product obtained in the above steps is continued to be annealed in an atmosphere containing ammonia gas.
  • the time for the continuous annealing treatment is preferably 0.5 to 2 hours, more preferably 0.7 to 1.8 hours, and more preferably 1.0 to 1.5 hours.
  • the temperature of the continuous annealing treatment is preferably 400 to 450°C, more preferably 410 to 440°C, and more preferably 420 to 430°C.
  • the heating rate of the continuous annealing treatment is preferably 5-10°C/min, more preferably 6-9°C/min, and more preferably 7-8°C/min.
  • the flow rate of the ammonia-containing atmosphere is preferably 50-150 mL/min, more preferably 70-130 mL/min, and more preferably 90-110 mL/min.
  • the present invention is to better complete and refine the overall technical scheme, better ensure the structure and morphology of the 1T/2H-MoSe 2 @TiO 2 nanocomposite material, and improve the 1T/2H-MoSe 2 @TiO 2 nanocomposite material.
  • Photocatalytic performance the preparation method of the above-mentioned 1T/2H-MoSe 2 @TiO 2 nanocomposite can be specifically as follows:
  • Conductive glass was selected as the substrate for growing TiO nanorods, and tetrabutyl titanate was used as the titanium source to prepare a precursor liquid, which was transferred into a high-pressure reactor with a polytetrafluoroethylene liner and reacted for 15 to 24 hours . Finally, the samples were placed in a muffle furnace and annealed in an air atmosphere to obtain rutile phase TiO 2 .
  • the reaction temperature may be 150°C.
  • the annealing temperature may be 450°C.
  • the selenium powder solution and the sodium molybdate dihydrate solution are mixed and stirred to obtain a precursor solution. Transfer the precursor solution to the autoclave with the Teflon liner.
  • the TiO 2 material prepared in step (1) is immersed in the precursor solution of the polytetrafluoroethylene liner, and reacted for 0.5 to 2 hours. Finally, the samples were placed in a tube furnace and annealed in an argon atmosphere to obtain highly crystalline 2H-MoSe 2 @TiO 2 .
  • the stirring time may be 30 min.
  • the reaction temperature may be 180°C.
  • the annealing temperature may be 450°C.
  • the prepared 2H-MoSe 2 @TiO 2 sample was placed in a tube furnace and annealed in an NH 3 atmosphere for 0.5–2 h to obtain a 1T/2H-MoSe 2 @TiO 2 material.
  • the annealing temperature may be 400°C.
  • the precursor in the step (1), in the Ti source precursor liquid, the precursor is prepared with tetrabutyl titanate, hydrochloric acid and water, and the volume ratio can be controlled to be 0.4:10:10.
  • the selenium powder solution can be specifically prepared from 0.158 g of selenium powder and 5 mL of hydrazine hydrate.
  • the sodium molybdate dihydrate solution can be specifically prepared from 0.242 g of ammonium molybdate dihydrate and 25 mL of deionized water.
  • the heating rate may specifically be 10° C./min, and the flow rate of NH 3 may specifically be 100 mL/min.
  • TiO 2 nanorod array photocatalyst by hydrothermal method tetrabutyl titanate is used as the Ti source to prepare the precursor liquid, and the precursor liquid is transferred into a high pressure reactor with a polytetrafluoroethylene liner, and the reaction is carried out at 150 ° C for 15-24 h;
  • Fig. 1 is a schematic schematic diagram of the process for preparing 1T/2H-MoSe 2 @TiO 2 in the present invention.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material provided by the present invention is an all-solid-state Z-type heterojunction photocatalyst, which is a system in which semiconductor TiO 2 and 1T/2H-MoSe 2 are heterogeneously combined.
  • the 1T metal phase MoSe 2 was introduced in-situ between 2H-MoSe 2 by N doping.
  • N doping NH 3 is selected as the N source, and the annealing time is preferably 0.5-2h.
  • TiO2 -based catalysts have the advantages of low toxicity, high conduction band gap and high chemical stability, although the construction-type heterojunction is an effective method to improve the photoelectric catalytic performance of TiO2 , photogenerated
  • the potential of holes in the valence band (VB) and the potential of electrons in the conduction band are also inevitably reduced, which is not conducive to the formation of active radicals, so maintaining the TiO2 band structure plays an important role in the production of hydrogen peroxide .
  • TiO 2 nanorods are first prepared on FTO by a hydrothermal method, rutile phase TiO 2 is obtained after annealing, and then MoSe 2 is modified on the TiO 2 nanorods by a hydrothermal method again to construct Z-type 2H-MoSe 2 @TiO 2 . Finally, by N-doping, part of 2H-MoSe 2 was converted into 1T-MoSe 2 , and the 1T/2H-MoSe 2 @TiO 2 all-solid-state Z-type heterostructure photocatalyst was constructed. The synthesis of 1T phase acts as a bridge for electron transfer, further promoting the separation of electron - hole pairs, which is more favorable for the production of H2O2.
  • the present invention also provides the 1T/2H-MoSe 2 @TiO 2 nanocomposite material described in any one of the above technical solutions or the 1T/2H-MoSe 2 @TiO 2 prepared by the preparation method described in any one of the above technical solutions Application of nanocomposites in the field of photocatalysts.
  • the all-solid-state Z-type heterostructure photocatalyst provided by the present invention is a system in which semiconductor TiO2 and MoSe2 are heterogeneously combined, MoSe2 nanoparticles are modified on TiO2 nanorods, and then a small part of 2H is annealed in an NH3 atmosphere.
  • the semiconductor phase MoSe 2 was transformed into 1T metal phase MoSe 2 , and the 1T/2H-MoSe 2 @TiO 2 all-solid Z-type photocatalyst was prepared.
  • the above steps of the present invention provide an in-situ synthesis of an all-solid-state Z-type heterostructure photocatalyst, a preparation method thereof, and an application in photoelectric catalysis to produce H 2 O 2 .
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material provided by the present invention has specific morphology, structure and Z-type heterostructure, and is obtained by combining semiconductor TiO 2 and 2H-MoSe 2 heterogeneity to obtain semiconductor TiO 2 Heterobinding system with MoSe 2 .
  • the invention combines hydrothermal method and element doping to prepare 1T/2H-MoSe 2 @TiO 2 all-solid-state Z-type heterojunction photocatalyst.
  • the semiconductor TiO 2 is heterogeneously combined with 2H-MoSe 2 , and a small part of 2H-MoSe 2 is converted into 1T-MoSe 2 in situ by doping, which is used as a bridge to transfer electrons to build a photoelectric catalytic system, which can greatly To improve the photocatalytic performance of the photocatalyst and increase the production of H 2 O 2 .
  • the nanocomposite material provided by the invention contains 2H semiconductor phase and 1T metal phase, and is a 1T/2H-MoSe 2 @TiO 2 all-solid Z-type composite material.
  • a photocatalyst a small part of 2H-MoSe 2 is converted into 1T- MoSe 2 , the synthesis of 1T phase acts as a bridge for electron transfer and further promotes the separation of electron-hole pairs. Therefore, the constructed photoelectric catalytic system can greatly improve the photoelectric catalytic performance, thereby increasing the production of H 2 O 2 . More conducive to the production of H 2 O 2 .
  • the preparation method provided by the invention is simple, the conditions are mild, and the process is controllable, which is beneficial to the realization of industrialization and has broad practical prospects.
  • the 1T/2H-MoSe 2 @TiO 2 nanocomposite material provided by the present invention is used as an all-solid Z-type composite system photocatalyst.
  • the all-solid Z-type system photocatalyst is prepared, which is used for photoelectric catalysis to prepare H 2 O 2 .
  • the FTO substrate needs to be cleaned, and the steps are ultrasonic cleaning in acetone, ethanol, and deionized water for 10 minutes in sequence.
  • Prepare the precursor solution of TiO2 transfer the precursor solution into the autoclave of the polytetrafluoroethylene liner, and then place the cleaned FTO on the polytetrafluoroethylene liner, and the conductive surface is inclined downward at a certain angle against the lining. After tightening the reactor, place it in a blast drying oven and react at 150°C for 15-24 hours. After natural cooling, the prepared samples were taken out and washed with deionized water and ethanol in turn.
  • the samples were placed in a vacuum drying oven to dry for 12 hours, and finally placed in a muffle furnace and annealed in an air atmosphere at 450 °C to obtain the rutile phase.
  • TiO 2 the heating rate was 2°C/min.
  • the TiO2 precursor solution was prepared with tetrabutyl titanate, hydrochloric acid and water, and the volume ratio was controlled to be 0.4:10:10. After the hydrochloric acid and water are mixed evenly, tetrabutyl titanate is added and stirred for 5 minutes before taking out.
  • the sodium molybdate dihydrate solution and the selenium powder solution were mixed and stirred for 30 min to obtain the MoSe 2 precursor solution.
  • the rutile TiO 2 material prepared in step (1) is immersed in the precursor solution of the polytetrafluoroethylene liner, the side where the TiO 2 is grown is leaning against the liner, and the reaction kettle is tightened and placed in a blast drying oven , the program set the heating rate as 3°C/min, the reaction temperature at 180°C, and the reaction time from 0.5 to 2 hours, 30 min, 60 min, 90 min and 120 min, respectively, to prepare 4 groups of samples. After the reaction was completed, it was naturally cooled to room temperature and taken out.
  • the prepared samples were taken out and washed with deionized water and ethanol in turn, then placed in a vacuum drying oven to dry for 12 hours, and finally placed in a tube furnace and annealed under an argon atmosphere at 450 °C to obtain highly crystalline 2H- MoSe 2 @TiO 2 .
  • the ammonium molybdate aqueous solution was prepared by mixing 0.242 g of ammonium molybdate dihydrate with 25 mL of deionized water, and magnetically stirring for 30 min.
  • the selenium powder aqueous solution was prepared by mixing 0.158 g of selenium powder with 5 mL of hydrazine hydrate, and then ultrasonicated for 5 min to make the mixture uniform.
  • the molar ratio of Mo and Se is 1:2.
  • the prepared 2H-MoSe 2 @TiO 2 sample was placed in a tube furnace and annealed at 400 °C for 0.5 to 2 h in an NH 3 atmosphere to obtain the 1T/2H-MoSe 2 @TiO 2 material.
  • the flow rate of NH3 was controlled at 100 mL/min, and the heating rate was controlled at 10 °C/min.
  • the final annealing time of 1T/2H-MoSe 2 @TiO 2 photocatalyst is 1 h.
  • the 1T/2H-MoSe 2 @TiO 2 composite material prepared by the present invention was characterized.
  • FIG. 2 is a scanning electron microscope image of TiO 2 , 2H-MoSe 2 @TiO 2 and 1T/2H-MoSe 2 @TiO 2 prepared by the present invention.
  • (a, d) are TiO 2
  • (b, e) are 2H-MoSe 2 @TiO 2
  • (c, f) are 1T/2H-MoSe 2 @TiO 2 .
  • FIG. 3 is a TEM image, HRTEM image and element Mapping image of the 1T metal phase and the 2H semiconductor phase coexisting in MoSe 2 nanoparticles and successfully modified on TiO 2 prepared in the embodiment of the present invention.
  • a is the TEM image
  • d is the element Mapping image.
  • TiO 2 prepared 2H-MoSe 2 @TiO 2 , 1T/2H-MoSe 2 @TiO 2 were used as photoanode materials, Pt sheet was used as counter electrode, and Ag/AgCl was used as reference electrode.
  • the reaction tank is a quartz cell.
  • the three-electrode system is connected with an ultraviolet lamp source, a peristaltic pump, an oxygen source and an electrochemical workstation to form a photoelectric catalytic test system.
  • the aqueous solution samples under different reaction times can be taken out through the peristaltic pump for H 2 O 2 concentration detection.
  • the detection method used the iodine reduction method.
  • the steps are to take 1 mL of the reaction solution, add 1 mL of KI (0.1M) and 50 ⁇ L of ammonium molybdate (0.01M) solution, mix evenly, and let stand for 15 minutes to complete the reaction. Finally, use a UV-Vis spectrophotometer to test the absorbance. The test result will have an absorption peak at 353nm, and then compare the calibration curve to obtain the concentration of H 2 O 2 .
  • the performance test of MoSe 2 @TiO 2 photocatalyst is shown in Figures 4-6.
  • Fig. 4 shows the transient photocurrent curves of 2H-MoSe 2 @TiO 2 prepared in the embodiment of the present invention with different hydrothermal times.
  • FIG. 5 is a histogram of the concentration of H 2 O 2 generated by 2H-MoSe 2 @TiO 2 with different hydrothermal times prepared in the embodiment of the present invention.
  • the highest H 2 O 2 yield is the 2H-MoSe 2 @TiO 2 sample with a hydrothermal time of 1 h.
  • FIG. 6 is a comparison diagram of the H 2 O 2 yield of 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention and other catalysts or no catalysts.
  • Figure (a) is the change curve of H 2 O 2 generation concentration with time under the condition of no light and light.
  • Figure (b) is the net production of H 2 O 2 for different samples after removing the H 2 O 2 produced by the blank sample.
  • FIG. 7 is a comparison diagram of the photoelectric catalytic degradation ability of 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention and other catalysts or catalyst-free photoelectric catalytic degradation of H 2 O 2 .
  • FIG. 8 is a cycle stability test diagram of H 2 O 2 prepared from 1T/2H-MoSe 2 @TiO 2 prepared in Example 1 of the present invention.

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Abstract

本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料，包括TiO 2纳米棒以及复合在TiO 2纳米棒上的MoSe 2纳米颗粒；所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒；所述混合相包含1T金属相和2H半导体相。本发明提供的复合材料是一种全固态Z型复合体系光催化剂，小部分的2H-MoSe 2转变成1T-MoSe 2，1T相的合成充当电子转移的桥梁，进一步促进电子-空穴对的分离，因而构筑的光电催化体系，能够很大程度的提高光电催化性能，进而增大H 2O 2的产量，更有利于H 2O 2的生产。而且本发明提供的制备方法简单，条件温和，过程可控，有利于工业化实现，具有广阔的实用前景。

Description

原位合成的全固态Z型异质结构光催化剂及其制备方法、光电催化合成H 2O 2中的应用
本申请要求于2021年03月25日提交中国专利局、申请号为202110321216.8、发明名称为“原位合成的全固态Z型异质结构光催化剂及其制备方法、光电催化合成H 2O 2中的应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于光电催化合成H 2O 2技术领域，涉及一种1T/2H-MoSe 2@TiO 2纳米复合材料及其制备方法、应用，尤其涉及一种原位合成的全固态Z型异质结构光催化剂及其制备方法、光电催化生产H 2O 2中的应用。
背景技术
目前工业合成过氧化氢(H 2O 2)的方法主要有蒽醌法和氢气(H 2)与氧气(O 2)直接合成，但是蒽醌法涉及不同的加氢和氧化反应，消耗了大量的有机溶剂和能量，而H 2与O 2直接合成容易发生爆炸。因此，业内一直需要找到一种安全，环保，节能的合成H 2O 2的有效方法。近年来，诸多研究人员已经提出了许多可行的生产H 2O 2的方法。光催化技术由于其安全、环保和节能等优点成为生产H 2O 2最有前途的方法之一，其主要依赖于以水(H 2O)和O 2为原料在半导体材料上产生H 2O 2，因为半导体材料在光照射条件下产生的电子可以还原O 2生成H 2O 2。在此过程中可以分为连续的两步单步电子氧还原，如反应式(1)和反应(2)，或O 2的直接两电子还原，如反应式(3)。
O 2+e -→·O 2 -(-0.33Vvs.NHE)        (1)
·O 2 -+2H ++e -→H 2O 2      (2)
O 2+2H ++2e -→H 2O 2(0.68Vvs.NHE)      3)
此外，光电化学(PEC)还可作为还原O 2生产H 2O 2的有效方法。在PEC体系中，半导体材料在光激发下可以产生电子-空穴对，然后导带电子可以通过施加偏压将电子转移到对电极还原O 2生成H 2O 2，因而可以更有效地分离电子-空穴对。
目前已提出许多替代性光催化剂将O 2还原为H 2O 2，例如石墨C 3N 4，CdS/ 石墨烯，WO 3和二氧化钛(TiO 2)。在这些半导体催化剂中，基于TiO 2的光催化剂由于其低毒性、高导带边隙和高化学稳定性而被广泛研究。但是，TiO 2光催化制备H 2O 2的产率低，这可归因于以下三个主要原因：1)由于固有的宽带隙(约3.2eV)，吸收光谱仅限于紫外线(UV)区域；2)光生电子和空穴的分离能力差，并且电子和空穴容易在体内重组；3)在光照下通过形成过氧化物(Ti-OOH)分解TiO 2表面上吸附的H 2O 2。
因此，如何找到一种更加适宜的方法，克服上述这些严重的缺点，改善TiO 2的性能，已成为本领域技术人员广泛关注的焦点之一。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种1T/2H-MoSe 2@TiO 2纳米复合材料及其制备方法、应用，特别是一种原位合成的全固态Z型异质结构光催化剂，本发明制备的1T/2H-MoSe 2@TiO 2纳米复合材料，是半导体TiO 2与MoSe 2异质结合的体系，而且含有2H半导体相和1T金属相，是一种全固态Z型光催化剂，能够提高光催化剂的光电催化性能和增大H 2O 2的产量。而且制备方法简单，条件温和，过程可控，有利于工业化实现，具有广阔的实用前景。
本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料，包括TiO 2纳米棒以及复合在TiO 2纳米棒上的MoSe 2纳米颗粒；
所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒；
所述混合相包含1T金属相和2H半导体相。
优选的，所述TiO 2纳米棒的长度为1.8～2μm；
所述TiO 2纳米棒的直径为150～250nm；
所述1T/2H-MoSe 2@TiO 2纳米复合材料包括用于光电催化的1T/2H-MoSe 2@TiO 2纳米复合材料；
所述光电催化包括光电催化合成H 2O 2。
优选的，所述MoSe 2纳米颗粒的粒径为15～25nm；
所述复合包括包覆；
所述TiO 2包括金红石相的TiO 2；
所述1T/2H-MoSe 2@TiO 2纳米复合材料为全固态Z型异质结构光催化剂；
所述1T/2H-MoSe 2@TiO 2纳米复合材料由原料经水热法和元素掺杂后得到。
本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料的制备方法，包括以下步骤：
1)将导电基底置于TiO 2前驱体溶液中进行水热反应，再经过退火处理后，得到TiO 2纳米棒；
2)将硒粉溶液和钼酸盐溶液混合后，得到前驱体溶液，再将上述步骤得到的TiO 2纳米棒置于前驱体溶液再次水热反应，再次退火处理后，得到中间产物2H-MoSe 2@TiO 2；
3)在含有氨气的气氛下，将上述步骤得到的中间产物继续退火处理后，得到1T/2H-MoSe 2@TiO 2纳米复合材料。
优选的，所述导电基底置于的方式包括导电基底的导电面冲下，斜靠在反应容器内壁上；
所述TiO 2前驱体溶液包括钛源、酸和水；
所述钛源包括钛酸四丁酯；
所述酸包括盐酸；
所述钛源、酸和水的体积比为0.4：(5～15)：(5～15)。
优选的，所述水热反应的温度为150～180℃；
所述水热反应的时间为15～24小时；
所述退火处理包括在空气气氛下退火处理；
所述退火处理的时间为2～3小时；
所述退火处理的温度为400～500℃。
优选的，所述硒粉溶液包括硒粉的水合肼溶液；
所述硒粉和水合肼的质量体积比为(0.025～0.034)g：1mL；
所述钼酸盐溶液包括二水合钼酸钠水溶液；
所述二水合钼酸钠和水的质量体积比为(0.009～0.012)g：1mL；
所述硒粉和钼酸盐的质量比为(0.65～0.7)：1。
优选的，所述再次水热反应的温度为170～190℃；
所述再次水热反应的时间为0.5～2小时；
所述再次退火处理的时间为2～3小时；
所述再次退火处理的温度为400～450℃；
所述再次退火处理包括在氩气气氛下退火处理；
所述TiO 2纳米棒具有阵列结构。
优选的，所述继续退火处理的时间为0.5～2小时；
所述继续退火处理的温度为400～450℃；
所述继续退火处理的升温速率为5～10℃/min；
所述含有氨气的气氛的流速为50～150mL/min；
所述1T/2H-MoSe 2@TiO 2纳米复合材料具有阵列结构。
本发明还提供了上述技术方案任意一项所述的1T/2H-MoSe 2@TiO 2纳米复合材料或上述技术方案任意一项所述的制备方法所制备的1T/2H-MoSe 2@TiO 2纳米复合材料在光催化剂领域中的应用。
本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料，包括TiO 2纳米棒以及复合在TiO 2纳米棒上的MoSe 2纳米颗粒；所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒；所述混合相包含1T金属相和2H半导体相。与现有技术相比，本发明基于现有的半导体催化剂中，TiO 2的光催化剂虽然具有低毒性、高导带边隙和高化学稳定性等特点，但是光催化制备H 2O 2时存在产率低的缺陷，而目前针对于TiO 2的光催化剂的改性，如异质结的构造，贵金属的装饰和元素掺杂等等方式，同样存在不利于制备H 2O 2的问题。本发明经过研究认为，目前用于改善TiO 2光催化性能的方法主要是构筑Ⅱ型异质结，但是这种异质结构不利于活性自由基的形成，因而不利于制备H 2O 2(过氧化氢)。
本发明创造性的得到了1T/2H-MoSe 2@TiO 2纳米复合材料，该复合材料具有特定的形貌、结构和Z型异质结构，是将半导体TiO 2与2H-MoSe 2异质进行结合，得到的半导体TiO 2与MoSe 2异质结合的体系。本发明提供的纳米复合材料含有2H半导体相和1T金属相，是一种全固态Z型复合材料。本发明提供的复合材料作为光催化剂，小部分的2H-MoSe 2转变成1T-MoSe 2，1T相的合成充当电子转移的桥梁，进一步促进电子-空穴对的分离，因而构筑的光电催化体系，能够很大程度的提高光电催化性能，进而增大H 2O 2的产量，更有利于H 2O 2的生产。而且本发明提供的制备方法简单，条件温和，过程可控， 有利于工业化实现，具有广阔的实用前景。
本发明提供的1T/2H-MoSe 2@TiO 2纳米复合材料作为全固态Z型复合体系光催化剂，通过耦合2H-MoSe 2和TiO 2，此外进一步使用原位生成的方法引入1T金属相MoSe 2制备得到全固态Z型体系光催化剂，用于光电催化制备H 2O 2。
实验结果表明，本发明制备的1T/2H-MoSe 2@TiO 2纳米复合材料，作为一种原位合成全固态Z型异质结构光催化剂，具有更好的光电催化性能生产H 2O 2。
附图说明
图1为本发明制备1T/2H-MoSe 2@TiO 2的流程示意简图；
图2为本发明制备的TiO 2、2H-MoSe 2@TiO 2和1T/2H-MoSe 2@TiO 2的扫描电镜图；
图3为本发明实施例制备的1T金属相和2H半导体相共存于MoSe 2纳米颗粒中和成功修饰到TiO 2上的TEM图、HRTEM图以及元素Mapping图；
图4本发明实施例制备的不同水热时间的2H-MoSe 2@TiO 2的瞬态光电流曲线图；
图5本发明实施例制备的不同水热时间的2H-MoSe 2@TiO 2生成的H 2O 2浓度柱状图；
图6为本发明实施例1制备的1T/2H-MoSe 2@TiO 2与其他催化剂或无催化剂的H 2O 2产量对比图；
图7为本发明实施例1制备的1T/2H-MoSe 2@TiO 2与其他催化剂或无催化剂的光电催化降解H 2O 2的能力对比图；
图8为本发明实施例1制备的1T/2H-MoSe 2@TiO 2制备H 2O 2的循环稳定性测试图。
具体实施方式
为了进一步了解本发明，下面结合实施例对本发明的优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点而不是对本发明专利要求的限制。
本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
本发明所用原料，对其纯度没有特别限制，本发明优选为分析纯或光催化剂制备领域的常规纯度即可。
本发明所有原料，其牌号和简称均属于本领域常规牌号和简称，每个牌号和简称在其相关用途的领域内均是清楚明确的，本领域技术人员根据牌号、简称以及相应的用途，能够从市售中购买得到或常规方法制备得到。
本发明所有工艺，其简称均属于本领域的常规简称，每个简称在其相关用途的领域内均是清楚明确的，本领域技术人员根据简称，能够理解其常规的工艺步骤。
本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料，包括TiO 2纳米棒以及复合在TiO 2纳米棒上的MoSe 2纳米颗粒；
所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒；
所述混合相包含1T金属相和2H半导体相。
本发明所述1T/2H-MoSe 2@TiO 2纳米复合材料，包括TiO 2纳米棒。
在本发明中，所述TiO 2纳米棒的长度优选为1.8～2μm，更优选为1.82～1.98μm，更优选为1.85～1.95μm，更优选为1.87～1.93μm。
在本发明中，所述TiO 2纳米棒的直径优选为150～250nm，更优选为170～230nm，更优选为190～210nm。
本发明所述的1T/2H-MoSe 2@TiO 2纳米复合材料，还包括复合在TiO 2纳米棒上的MoSe 2纳米颗粒。在本发明中，所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒。所述MoSe 2纳米颗粒为混合相，所述混合相包含1T金属相和2H半导体相。
在本发明中，所述MoSe 2纳米颗粒的粒径优选为15～25nm，更优选为17～23nm，更优选为19～21nm。
在本发明中，所述复合具体可以为包覆。
在本发明中，所述TiO 2优选包括金红石相的TiO 2。
在本发明中，所述TiO 2纳米棒具有阵列结构。进而，所述1T/2H-MoSe 2@TiO 2纳米复合材料同样具有阵列结构。
在本发明中，所述1T/2H-MoSe 2@TiO 2纳米复合材料优选包括用于光电催化的1T/2H-MoSe 2@TiO 2纳米复合材料。具体的，所述1T/2H-MoSe 2@TiO 2纳 米复合材料优选为全固态Z型异质结构光催化剂。更具体的，所述光电催化优选包括光电催化合成H 2O 2。
在本发明中，所述1T/2H-MoSe 2@TiO 2纳米复合材料由原料经水热法和元素掺杂后得到。
本发明提供了一种1T/2H-MoSe 2@TiO 2纳米复合材料的制备方法，包括以下步骤：
1)将导电基底置于TiO 2前驱体溶液中进行水热反应，再经过退火处理后，得到TiO 2纳米棒；
2)将硒粉溶液和钼酸盐溶液混合后，得到前驱体溶液，再将上述步骤得到的TiO 2纳米棒置于前驱体溶液再次水热反应，再次退火处理后，得到中间产物2H-MoSe 2@TiO 2；
3)在含有氨气的气氛下，将上述步骤得到的中间产物继续退火处理后，得到1T/2H-MoSe 2@TiO 2纳米复合材料。
本发明首先将导电基底置于TiO 2前驱体溶液中进行水热反应，再经过退火处理后，得到TiO 2纳米棒。
在本发明中，所述导电基底优选包括导电玻璃(FTO)。
在本发明中，所述导电基底置于的方式优选包括导电基底的导电面冲下，斜靠在反应容器内壁上。
在本发明中，所述TiO 2前驱体溶液优选包括钛源、酸和水。其中，所述钛源优选包括钛酸四丁酯。所述酸优选包括盐酸。
在本发明中，所述钛源和酸的体积比优选为0.4：(5～15)，更优选为0.4：(7～13)，更优选为0.4：(9～11)。
在本发明中，所述钛源和水的体积比优选为0.4：(5～15)，更优选为0.4：(7～13)，更优选为0.4：(9～11)。
在本发明中，所述水热反应的温度优选为150～180℃，更优选为155～175℃，更优选为160～170℃。
在本发明中，所述水热反应的时间优选为15～24小时，更优选为17～22小时，更优选为19～20小时。
在本发明中，所述退火处理优选包括在空气气氛下退火处理。
在本发明中，所述退火处理的时间优选为2～3小时，更优选为2.2～2.8小时，更优选为2.4～2.6小时。
在本发明中，所述退火处理的温度优选为400～500℃，更优选为420～480℃，更优选为440～460℃。
本发明随后将硒粉溶液和钼酸盐溶液混合后，得到前驱体溶液，再将上述步骤得到的TiO 2纳米棒置于前驱体溶液再次水热反应，再次退火处理后，得到中间产物2H-MoSe 2@TiO 2。
在本发明中，所述硒粉溶液优选包括硒粉的水合肼溶液。
在本发明中，所述硒粉和水合肼的质量体积比优选为(0.025～0.034)g：1mL，更优选为(0.027～0.032)g：1mL，更优选为(0.029～0.030)g：1mL。
在本发明中，所述钼酸盐溶液优选包括二水合钼酸钠水溶液。
在本发明中，所述二水合钼酸钠和水的质量体积比优选为(0.009～0.012)g：1mL，更优选为(0.009～0.011)g：1mL，更优选为(0.01～0.012)g：1mL。
在本发明中，所述硒粉和钼酸盐的质量比优选为(0.65～0.7)：1，更优选为(0.66～0.69)：1，更优选为(0.67～0.68)：1。
在本发明中，所述再次水热反应的温度优选为170～190℃，更优选为172～188℃，更优选为175～185℃，更优选为177～183℃。
在本发明中，所述再次水热反应的时间优选为0.5～2小时，更优选为0.7～1.8小时，更优选为1.0～1.5小时。
在本发明中，所述再次退火处理的时间优选为2～3小时，更优选为2.2～2.8小时，更优选为2.4～2.6小时。
在本发明中，所述再次退火处理的温度优选为400～450℃，更优选为410～440℃，更优选为420～430℃。
在本发明中，所述退火处理优选包括在氩气气氛下退火处理。
本发明最后在含有氨气的气氛下，将上述步骤得到的中间产物继续退火处理后，得到1T/2H-MoSe 2@TiO 2纳米复合材料。
在本发明中，所述继续退火处理的时间优选为0.5～2小时，更优选为0.7～1.8小时，更优选为1.0～1.5小时。
在本发明中，所述继续退火处理的温度优选为400～450℃，更优选为 410～440℃，更优选为420～430℃。
在本发明中，所述继续退火处理的升温速率优选为5～10℃/min，更优选为6～9℃/min，更优选为7～8℃/min。
在本发明中，所述含有氨气的气氛的流速优选为50～150mL/min，更优选为70～130mL/min，更优选为90～110mL/min。
本发明为更好的完整和细化整体技术方案，更好的保证1T/2H-MoSe 2@TiO 2纳米复合材料的结构和形貌，提高1T/2H-MoSe 2@TiO 2纳米复合材料的光催化性能，上述1T/2H-MoSe 2@TiO 2纳米复合材料的制备方法具体可以为以下步骤：
(1)水热法制备TiO 2纳米棒材料：
选择导电玻璃(FTO)作为生长TiO 2纳米棒的基板，将钛酸四丁酯作为钛源制备得到前驱体液，将前驱体液移入聚四氟乙烯内胆的高压反应釜中，反应15～24小时。最后将样品置于马弗炉中在空气气氛下退火得到金红石相TiO 2。具体的，反应温度可以为150℃。退火温度可以为450℃。
(2)水热法制备2H-MoSe 2@TiO 2材料：
将硒粉溶液和二水合钼酸钠溶液混合，搅拌得到前驱体溶液。将前驱体溶液转移到聚四氟乙烯内胆的高压反应釜中。将步骤(1)制备的TiO 2材料浸渍于聚四氟乙烯内胆的前驱体溶液，反应0.5～2小时。最后将样品置于管式炉中在氩气气氛下，退火得到高结晶的2H-MoSe 2@TiO 2。具体的，搅拌时间可以为30min。反应温度可以为180℃。退火温度可以为450℃。
(3)N掺杂制备1T/2H-MoSe 2@TiO 2材料：
将制备得到的2H-MoSe 2@TiO 2样品放置在管式炉中，在NH 3气氛下退火0.5～2小时，得到1T/2H-MoSe 2@TiO 2材料。具体的，退火温度可以为400℃。
其中，所述步骤(1)中，所述Ti源前驱体液中，前驱体用钛酸四丁酯、盐酸和水配制，控制其体积比可以为0.4:10:10。
其中，所述步骤(2)中，所述硒粉溶液具体可以由0.158g硒粉和5mL水合肼配制。所述二水合钼酸钠溶液具体可以由0.242g二水合钼酸铵和25mL去离子水配制。
其中，所述步骤(3)中，所述退火条件中，升温速率具体可以为10℃/min， NH 3流速具体可以为100mL/min。
优选的，
水热法制备TiO 2纳米棒阵列光催化剂：选用钛酸四丁酯作为Ti源制备前驱液，将前驱体液移入聚四氟乙烯内胆的高压反应釜中，在150℃下反应15～24h；
水热法制备2H-MoSe 2@TiO 2光催化剂：将上述步骤制备的TiO 2光催化剂浸渍于Se粉和二水合钼酸钠混合溶液中，静置1小时后进行水热处理。最后在氩气气氛下高温退火。
N掺杂制备1T/2H-MoSe 2@TiO 2光催化剂:将上述步骤制备的2H-MoSe 2@TiO 2光催化剂放置于管式炉中，在NH 3气氛下退火1小时。
参见图1，图1为本发明制备1T/2H-MoSe 2@TiO 2的流程示意简图。
本发明提供的1T/2H-MoSe 2@TiO 2纳米复合材料是一种全固态Z型异质结光催化剂，是半导体TiO 2与1T/2H-MoSe 2异质结合的体系，在TiO 2与2H-MoSe 2之间通过N掺杂的方法原位引入1T金属相MoSe 2。N掺杂选用NH 3作为N源，退火时间优选为0.5～2h。
本发明研究认为，虽然TiO 2基催化剂具有低毒、高导带边隙和高化学稳定性等优点，尽管构筑型异质结是一种有效的方法来改善TiO 2的光电催化性能，但光生空穴在价带(VB)的电势和电子在导带的电势也不可避免地降低，从而不利于活性自由基的形成，因此保持TiO 2能带结构对过氧化氢的生产起着重要的作用。本发明先通过水热法在FTO上制备TiO 2纳米棒，经退火后得到金红石相的TiO 2，随后再次通过水热法将MoSe 2修饰到TiO 2纳米棒上，构筑得到Z型2H-MoSe 2@TiO 2。最后通过N掺杂的方法，将部分的2H-MoSe 2转变成1T-MoSe 2，构筑得到1T/2H-MoSe 2@TiO 2全固态Z型异质结构光催化剂。1T相的合成充当电子转移的桥梁，进一步促进电子-空穴对的分离，从而更有利于H 2O 2的生产。
本发明还提供了上述技术方案任意一项所述的1T/2H-MoSe 2@TiO 2纳米复合材料或上述技术方案任意一项所述的制备方法所制备的1T/2H-MoSe 2@TiO 2纳米复合材料在光催化剂领域中的应用。
本发明提供的全固态Z型异质结构光催化剂是半导体TiO 2与MoSe 2异质 结合的体系，在TiO 2纳米棒上修饰MoSe 2纳米颗粒，随后通过在NH 3气氛下退火将小部分2H半导体相MoSe 2转变成1T金属相MoSe 2，制备得到1T/2H-MoSe 2@TiO 2全固态Z型光催化剂。
本发明上述步骤提供了一种原位合成的全固态Z型异质结构光催化剂及其制备方法、光电催化生产H 2O 2中的应用。本发明提供的1T/2H-MoSe 2@TiO 2纳米复合材料具有特定的形貌、结构和Z型异质结构，是将半导体TiO 2与2H-MoSe 2异质进行结合，得到的半导体TiO 2与MoSe 2异质结合的体系。本发明将水热法和元素掺杂结合，制备出了1T/2H-MoSe 2@TiO 2全固态Z型异质结光催化剂。将半导体TiO 2与2H-MoSe 2异质结合，并通过掺杂的办法原位将小部分2H-MoSe 2转变成1T-MoSe 2，以此作为转移电子的桥梁构筑光电催化体系，可以很大程度提高光催化剂的光电催化性能和增大H 2O 2的产量。
本发明提供的纳米复合材料含有2H半导体相和1T金属相，是一种1T/2H-MoSe 2@TiO 2全固态Z型复合材料，作为光催化剂，小部分的2H-MoSe 2转变成1T-MoSe 2，1T相的合成充当电子转移的桥梁，进一步促进电子-空穴对的分离，因而构筑的光电催化体系，能够很大程度的提高光电催化性能，进而增大H 2O 2的产量，更有利于H 2O 2的生产。而且本发明提供的制备方法简单，条件温和，过程可控，有利于工业化实现，具有广阔的实用前景。
本发明提供的1T/2H-MoSe 2@TiO 2纳米复合材料作为全固态Z型复合体系光催化剂，通过耦合2H-MoSe 2和TiO 2，此外进一步使用原位生成的方法引入1T金属相MoSe 2制备得到全固态Z型体系光催化剂，用于光电催化制备H 2O 2。
实验结果表明，本发明制备的提出的1T/2H-MoSe 2@TiO 2纳米复合材料，作为一种原位合成全固态Z型异质结构光催化剂，具有更好的光电催化性能生产H 2O 2。
为了进一步说明本发明，以下结合实施例对本发明提供的一种1T/2H-MoSe 2@TiO 2纳米复合材料及其制备方法、应用进行详细描述，但是应当理解，这些实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制，本发明的保护范围也不限于下述的实施例。
实施例
(1)水热法制备TiO 2材料：
FTO基底需要进行清洗，其步骤为依次在丙酮、乙醇、去离子水中超声清洗10min。制备TiO 2的前驱体溶液，将前驱体溶液转入聚四氟乙烯内胆的高压反应釜中，随后将清洗后的FTO放置到聚四氟乙烯内衬，导电面以一定的角度朝下斜靠在内衬上。将反应釜拧紧后放置于鼓风干燥箱中，在150℃下反应15-24小时。待自然冷却后将制备得到的样品取出依次用去离子水和乙醇清洗干净，随后将样品放置在真空干燥箱中干燥12小时，最后置于马弗炉中在450℃空气气氛下退火得到金红石相TiO 2，升温速率为2℃/min。
其中TiO 2的前驱体溶液用钛酸四丁酯、盐酸和水配制，控制其体积比为0.4:10:10。盐酸和水混合均匀后加入钛酸四丁酯搅拌5min后即可取出。
(2)水热法制备2H-MoSe 2@TiO 2材料：
将二水合钼酸钠溶液和硒粉溶液混合，搅拌30min得到MoSe 2前驱体溶液。将前驱体溶液转移到聚四氟乙烯内胆的高压反应釜中。将步骤(1)制备的金红石TiO 2材料浸渍于聚四氟乙烯内胆的前驱体溶液，生长TiO 2的一面朝下斜靠在内衬上，拧紧反应釜后放置于鼓风干燥箱中，程序设定升温速率为3℃/min，反应温度为180℃，反应时间从0.5～2小时，分别为30min、60min、90min以及120min，制备4组样品。待反应结束后自然冷却至室温取出。将制备得到的样品分别取出依次用去离子水和乙醇清洗，随后将样品放置在真空干燥箱中干燥12小时，最后置于管式炉中在450℃氩气气氛下退火得到高结晶的2H-MoSe 2@TiO 2。
其中钼酸铵水溶液的制备为0.242g二水合钼酸铵与25mL去离子水混合，磁力搅拌30min。硒粉水溶液的制备为0.158g硒粉与5mL水合肼混合后超声5min使其混合均匀。另外，所述前驱体溶液中，Mo与Se的摩尔比为1:2。
(3)N掺杂制备1T/2H-MoSe 2@TiO 2材料：
将制备得到的2H-MoSe 2@TiO 2样品放置在管式炉中，在NH 3气氛下400℃退火0.5～2小时得到1T/2H-MoSe 2@TiO 2材料。
其中，NH 3的流速控制在100mL/min，升温速率控制在10℃/min。最终 1T/2H-MoSe 2@TiO 2光催化剂退火时间为1h时为最佳。
对本发明制备的1T/2H-MoSe 2@TiO 2复合材料进行表征。
参见图2，图2为本发明制备的TiO 2、2H-MoSe 2@TiO 2和1T/2H-MoSe 2@TiO 2的扫描电镜图。
其中，(a，d)为TiO 2，(b，e)为2H-MoSe 2@TiO 2，(c，f)为1T/2H-MoSe 2@TiO 2。
参见图3，图3为本发明实施例制备的1T金属相和2H半导体相共存于MoSe 2纳米颗粒中和成功修饰到TiO 2上的TEM图、HRTEM图以及元素Mapping图。
其中，a为TEM图、(b，c)HRTEM图以及d为元素Mapping图。
对本发明实施例1制备的1T/2H-MoSe 2@TiO 2复合材料进行性能检测。
光电催化制备H 2O 2性能测试：
将TiO 2、制备得到的2H-MoSe 2@TiO 2、1T/2H-MoSe 2@TiO 2充当光阳极材料，Pt片充当对电极，Ag/AgCl充当参比电极。反应池选用石英池。将三电极体系与紫外灯源、蠕动泵、氧气源和电化学工作站相连，组成光电催化测试系统，通过蠕动泵可将不同反应时间下的水溶液样品取出进行H 2O 2浓度检测，其浓度的检测方法使用碘还原法。其步骤为取1mL反应溶液，加入1mL KI(0.1M)和50μL的钼酸铵(0.01M)溶液，混合均匀后静置15min至完全反应。最后使用紫外可见分光光度计进行吸光度测试，测试结果会在353nm处出现吸收峰，再对比校正曲线即可得出H 2O 2的浓度。MoSe 2@TiO 2光催化剂的性能测试如图4～6所示。
参见图4，图4本发明实施例制备的不同水热时间的2H-MoSe 2@TiO 2的瞬态光电流曲线图。
参见图5，图5本发明实施例制备的不同水热时间的2H-MoSe 2@TiO 2生成的H 2O 2浓度柱状图。
其中，H 2O 2产量最高为水热时间是1小时的2H-MoSe 2@TiO 2样品。
参见图6，图6为本发明实施例1制备的1T/2H-MoSe 2@TiO 2与其他催化剂或无催化剂的H 2O 2产量对比图。
其中，图(a)是在无光和有光照条件下，H 2O 2生成浓度随时间的变化曲 线。图(b)是去掉空白样品产生的H 2O 2后的不同样品净生成H 2O 2的产量。
由图6可知，1T/2H-MoSe 2@TiO 2的H 2O 2产量可以达到TiO 2催化剂的4.7倍。
参见图7，图7为本发明实施例1制备的1T/2H-MoSe 2@TiO 2与其他催化剂或无催化剂的光电催化降解H 2O 2的能力对比图。
由图7可知，在H 2O 2降解方面，1T/2H-MoSe 2@TiO 2的降解能力比TiO 2差。这表明1T/2H-MoSe 2@TiO 2对实时生成H 2O 2降解少，这也是H 2O 2产量提高的原因之一。
参见图8，图8为本发明实施例1制备的1T/2H-MoSe 2@TiO 2制备H 2O 2的循环稳定性测试图。
由图8可以看出，本发明制备的1T/2H-MoSe 2@TiO 2(60min水热和1小时退火)表现出良好的循环稳定性。
以上对本发明提供的一种原位合成的全固态Z型异质结构光催化剂及其制备方法、光电催化生产H 2O 2中的应用进行了详细的介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种1T/2H-MoSe 2@TiO 2纳米复合材料，其特征在于，包括TiO 2纳米棒以及复合在TiO 2纳米棒上的MoSe 2纳米颗粒；
    所述MoSe 2纳米颗粒包括混合相MoSe 2纳米颗粒；
    所述混合相包含1T金属相和2H半导体相。
  2. 根据权利要求1所述的1T/2H-MoSe 2@TiO 2纳米复合材料，其特征在于，所述TiO 2纳米棒的长度为1.8～2μm；
    所述TiO 2纳米棒的直径为150～250nm；
    所述1T/2H-MoSe 2@TiO 2纳米复合材料包括用于光电催化的1T/2H-MoSe 2@TiO 2纳米复合材料；
    所述光电催化包括光电催化合成H 2O 2。
  3. 根据权利要求1所述的1T/2H-MoSe 2@TiO 2纳米复合材料，其特征在于，所述MoSe 2纳米颗粒的粒径为15～25nm；
    所述复合包括包覆；
    所述TiO 2包括金红石相的TiO 2；
    所述1T/2H-MoSe 2@TiO 2纳米复合材料为全固态Z型异质结构光催化剂；
    所述1T/2H-MoSe 2@TiO 2纳米复合材料由原料经水热法和元素掺杂后得到。
  4. 一种1T/2H-MoSe 2@TiO 2纳米复合材料的制备方法，其特征在于，包括以下步骤：
    1)将导电基底置于TiO 2前驱体溶液中进行水热反应，再经过退火处理后，得到TiO 2纳米棒；
    2)将硒粉溶液和钼酸盐溶液混合后，得到前驱体溶液，再将上述步骤得到的TiO 2纳米棒置于前驱体溶液再次水热反应，再次退火处理后，得到中间产物2H-MoSe 2@TiO 2；
    3)在含有氨气的气氛下，将上述步骤得到的中间产物继续退火处理后，得到1T/2H-MoSe 2@TiO 2纳米复合材料。
  5. 根据权利要求4所述的制备方法，其特征在于，所述导电基底置于的 方式包括导电基底的导电面冲下，斜靠在反应容器内壁上；
    所述TiO 2前驱体溶液包括钛源、酸和水；
    所述钛源包括钛酸四丁酯；
    所述酸包括盐酸；
    所述钛源、酸和水的体积比为0.4：(5～15)：(5～15)。
  6. 根据权利要求4所述的制备方法，其特征在于，所述水热反应的温度为150～180℃；
    所述水热反应的时间为15～24小时；
    所述退火处理包括在空气气氛下退火处理；
    所述退火处理的时间为2～3小时；
    所述退火处理的温度为400～500℃。
  7. 根据权利要求4所述的制备方法，其特征在于，所述硒粉溶液包括硒粉的水合肼溶液；
    所述硒粉和水合肼的质量体积比为(0.025～0.034)g：1mL；
    所述钼酸盐溶液包括二水合钼酸钠水溶液；
    所述二水合钼酸钠和水的质量体积比为(0.009～0.012)g：1mL；
    所述硒粉和钼酸盐的质量比为(0.65～0.7)：1。
  8. 根据权利要求4所述的制备方法，其特征在于，所述再次水热反应的温度为170～190℃；
    所述再次水热反应的时间为0.5～2小时；
    所述再次退火处理的时间为2～3小时；
    所述再次退火处理的温度为400～450℃；
    所述再次退火处理包括在氩气气氛下退火处理；
    所述TiO 2纳米棒具有阵列结构。
  9. 根据权利要求4所述的制备方法，其特征在于，所述继续退火处理的时间为0.5～2小时；
    所述继续退火处理的温度为400～450℃；
    所述继续退火处理的升温速率为5～10℃/min；
    所述含有氨气的气氛的流速为50～150mL/min；
    所述1T/2H-MoSe 2@TiO 2纳米复合材料具有阵列结构。
  10. 权利要求1～4任意一项所述的1T/2H-MoSe 2@TiO 2纳米复合材料或权利要求5～9任意一项所述的制备方法所制备的1T/2H-MoSe 2@TiO 2纳米复合材料在光催化剂领域中的应用。
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