WO2022144043A1 - Mof衍生的氧化锌复合二氧化钛异质结的制备方法及光电分解水应用 - Google Patents

Mof衍生的氧化锌复合二氧化钛异质结的制备方法及光电分解水应用 Download PDF

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WO2022144043A1
WO2022144043A1 PCT/CN2022/078245 CN2022078245W WO2022144043A1 WO 2022144043 A1 WO2022144043 A1 WO 2022144043A1 CN 2022078245 W CN2022078245 W CN 2022078245W WO 2022144043 A1 WO2022144043 A1 WO 2022144043A1
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tio
zno
heterojunction
mof
zinc oxide
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徐东波
丁祺家
施伟东
范伟强
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江苏大学
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
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    • 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

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  • the invention belongs to the technical field of composite material preparation, and relates to the preparation of photoelectric catalysts, in particular to a preparation method of MOF-derived zinc oxide composite titanium dioxide (ZnO/TiO 2 ) heterojunction and application of photoelectric water splitting.
  • Hydrogen (H 2 ) has attracted extensive attention as a renewable, non-polluting emerging energy with high combustion calorific value.
  • solar-driven photoelectrochemical (PEC) water splitting for hydrogen production is an effective strategy to solve the current energy crisis and environmental problems.
  • PEC photoelectrochemical
  • exploring high-efficiency optoelectronic electrode materials is essential for practical applications.
  • TiO2 is considered as a promising PEC water-splitting photoelectrode material due to its stable structure, abundant content and low price.
  • the high electron/hole recombination rate and slow oxidation reaction kinetics greatly limit their optoelectronic performance.
  • TiO 2 rutile, 3.0 eV
  • heterojunctions is an effective semiconductor modification method.
  • Selecting a suitable metal oxide for compounding with TiO2 the formed heterostructure can significantly promote the separation of electrons/holes, improve the carrier migration behavior, and improve the utilization of sunlight.
  • Sun et al. found that the combination of TiO2 and Fe2O3 can significantly improve the PEC performance, using the hydrothermal method to grow Fe2O3 on TiO2 nanorods , the narrow band gap of Fe2O3 can enhance the light absorption, resulting in more More photogenerated carriers can effectively promote the decomposition of PEC water.
  • ZnO has received extensive attention due to its high electron mobility and low carrier recombination rate. Therefore, it can be used as an effective candidate material for the construction of TiO2 heterojunctions. It is worth mentioning that the band gap energies of ZnO and TiO are similar, so the constructed ZnO/ TiO heterostructure has many advantages. Ng et al. reported that the constructed heterojunction of ZnO composited on TiO2 nanotubes produced a distinct red shift in the photoresponse, thereby expanding the response range of the visible spectrum.
  • Metal-organic frameworks (MOFs) are used as sacrificial templates to generate metal oxides through calcination, which can promote water splitting.
  • MOFs provide the corresponding metal oxides with specific microstructures, while MOF-derived metal oxide materials can retain the characteristics of MOFs with large specific surface area and porous structure, thereby exposing more active sites, which can enhance the water splitting process. plays an important role in.
  • Zn-MOF ZIF-8
  • the invention discloses the preparation of a MOF-derived zinc oxide composite titanium dioxide (ZnO/TiO 2 ) heterojunction method.
  • a preparation method of MOF-derived zinc oxide composite titanium dioxide (ZnO/TiO 2 ) heterojunction comprising the following steps:
  • A. Preparation of TiO2 nanorod arrays Add tetrabutyl titanate to 3 mol/L HCl solution, mix and stir evenly at a volume ratio of 60:1 to 30:1, preferably 50:1, and transfer the mixture to the reaction
  • immerse the cleaned FTO glass sheet keep it at a constant temperature of 150-200 °C for 5-10 hours, preferably at a constant temperature of 180 °C for 6 hours, naturally cool it to room temperature, take it out, wash it with deionized water, and dry it, and then calcine it in a muffle furnace at 300-500 °C for 1- 4h, preferably calcined at 450°C for 2h to obtain FTO sheets loaded with TiO 2 ;
  • ZIF-8 precursor solution add 2-methylimidazole to the deionized aqueous solution of Zn(NO 3 ) 2 ⁇ 6H 2 O, and stir to obtain Zn-MOF (ZIF-8) ) solution, wherein the mass-volume ratio of the 2-methylimidazole, Zn(NO 3 ) 2 ⁇ 6H 2 O and deionized water is 0.5-0.8g:0.2-0.5g:60ml, preferably 0.66g:0.29g : 60ml;
  • ZnO/TiO 2 Preparation of ZnO/TiO 2 : Immerse the FTO sheet loaded with TiO 2 in Zn-MOF (ZIF-8) solution, soak it for 1-16 min, take it out, wash it with deionized water, and calcine at 300-500 °C 1 to 3 hours, preferably calcination at 350° C. for 2 hours, to obtain a zinc oxide composite titanium dioxide (ZnO/TiO 2 ) heterojunction.
  • ZIF-8 Zn-MOF
  • the cleaned FTO glass sheet in step A first clean the surface of the FTO glass sheet, then ultrasonically clean it in acetone, isopropyl alcohol and ethylene glycol for 0.5h respectively, take it out, and dry it in the air .
  • the prepared ZnO/TiO 2 heterojunction has uniform and regular TiO 2 nanorods with a size of about 2-3 ⁇ m, and the TiO 2 surface is obviously rough after compounding ZnO.
  • Another object of the present invention is to disclose the application of the prepared ZnO/TiO 2 heterojunction to photoelectric catalytic water splitting to produce hydrogen.
  • the ZnO/TiO 2 composite photoelectric catalyst prepared by the present invention uses X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and other instruments to analyze the morphology, structure and composition of the product.
  • XRD X-ray diffraction
  • SEM scanning electron microscope
  • XPS X-ray photoelectron spectroscopy
  • the absorbance was measured with a UV-Vis spectrophotometer, and the transient photocurrent and stability were measured with a standard three-electrode electrochemical workstation to evaluate its photocatalytic activity.
  • the reactant reagents used in the present invention are all commercially available.
  • the inventors prepared a ZnO/ TiO heterojunction by an electrostatic adsorption process.
  • the Zeta potential of TiO was -31.98mV, while the Zeta potential of Zn-MOF (ZIF-8) was 39mV.
  • the two can be firmly combined, and then the Zn-MOF (ZIF-8) can be converted into ZnO by pyrolysis treatment, thereby preparing the ZnO/TiO 2 composite photoelectric catalyst.
  • the present invention utilizes hydrothermal method, soaking method and calcination treatment to synthesize ZnO/ TiO2 heterojunction, ZnO derived from Zn-MOF (ZIF-8) is compounded on the surface of TiO2 nanorod, and effectively strengthens the ZnO/ TiO2 heterojunction
  • ZIF-8 Zn-MOF
  • the carrier migration rate of the composite photocatalyst improves the electron-hole separation efficiency, enhances the light capture ability of the catalyst, and improves the photoelectric catalytic performance of the heterojunction composite photocatalyst.
  • the prepared ZnO/TiO 2 catalyst is suitable for environmental and energy It has good application prospects in other fields, especially in photoelectric catalytic water splitting for hydrogen production.
  • Fig. 1 XRD diffraction pattern of the ZnO/TiO 2 composite photoelectric catalyst prepared in Example 1;
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. Prepare a HCl solution with a molar concentration of 3 mol/L, then add 1.2 mL of tetrabutyl titanate to the solution, mix and stir evenly, transfer the mixture to a reaction kettle, immerse it in a cleaned FTO glass sheet, and keep the temperature at 180 °C for 6 h , naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 450 °C for 2 h;
  • Zn-MOF (ZIF-8) precursor take 0.66g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.29g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the XPS diagram contains the existence of Ti, O, Zn elements and the corresponding valence states, which proves that ZnO is effectively prepared;
  • the nanorod morphology of TiO2 as well as ZnO are uniformly attached to the surface of TiO2 ;
  • pure TiO exhibits a narrow absorbance at 410 nm, while the absorption edge of the ZnO/ TiO heterojunction photocatalyst exhibits an obvious red shift
  • the ZnO/ TiO2 heterojunction composite photoelectric catalyst has good stability.
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. Prepare a HCl solution with a molar concentration of 3 mol/L, then add 1 mL of tetrabutyl titanate to the solution, mix and stir evenly, transfer the mixture to a reaction kettle, immerse it in a cleaned FTO glass sheet, and keep it at 200°C for 7 hours. Naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 400°C for 3h;
  • Zn-MOF (ZIF-8) precursor take 0.5g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.2g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • ZnO/TiO 2 Preparation of ZnO/TiO 2 : Immerse the FTO sheet loaded with TiO 2 in Zn-MOF (ZIF-8) solution, soak for 1, 3, 5 minutes, take out, rinse with deionized water, muffle furnace 300 After calcination at °C for 1 h, the ZnO/TiO 2 composite photoelectric catalyst was obtained.
  • ZIF-8 Zn-MOF
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.79 mA/cm 2 (1.23 V vs RHE).
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. Prepare a HCl solution with a molar concentration of 3 mol/L, then add 1.5 mL of tetrabutyl titanate to the solution, mix and stir evenly, transfer the mixture to a reaction kettle, immerse it in a clean FTO glass sheet, and keep it at 200 °C for 7 h , naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 350 °C for 2 h;
  • Zn-MOF (ZIF-8) precursor take 0.55g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.25g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.87 mA/cm 2 (1.23 V vs RHE).
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. Prepare a HCl solution with a molar concentration of 3 mol/L, then add 2 mL of tetrabutyl titanate to the solution, mix and stir evenly, transfer the mixture to a reaction kettle, immerse it in a cleaned FTO glass sheet, and keep it at 150 °C for 10 h. Naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 500 °C for 4 hours;
  • Zn-MOF (ZIF-8) precursor take 0.7g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.3g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.53 mA/cm 2 (1.23 V vs RHE).
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. Prepare a HCl solution with a molar concentration of 3 mol/L, then add 1.5 mL of tetrabutyl titanate to the solution, mix and stir evenly, transfer the mixture to a reaction kettle, immerse it in a clean FTO glass sheet, and keep it at 170 °C for 7 hours , naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 420 °C for 4 h;
  • Zn-MOF (ZIF-8) precursor take 0.6g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.4g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.93 mA/cm 2 (1.23 V vs RHE).
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. A HCl solution with a molar concentration of 3 mol/L was prepared, and then 3 mL of tetrabutyl titanate was added to the solution, mixed and stirred evenly, and the mixture was transferred to a reaction kettle, immersed in a cleaned FTO glass sheet, and kept at a constant temperature of 190 °C for 6 h. Naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 460 °C for 3 hours;
  • Zn-MOF (ZIF-8) precursor take 0.8g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.5g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.67 mA/cm 2 (1.23 V vs RHE).
  • A. Preparation of TiO nanorod arrays FTO glass sheets were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 h, respectively. A HCl solution with a molar concentration of 3 mol/L was prepared, and then 3 mL of tetrabutyl titanate was added to the solution, mixed and stirred evenly, and the mixture was transferred to a reaction kettle, immersed in a cleaned FTO glass sheet, and kept at a constant temperature of 190 °C for 6 h. Naturally cooled to room temperature, taken out, washed with deionized water, dried, and then calcined in a muffle furnace at 480 °C for 1 h;
  • Zn-MOF (ZIF-8) precursor take 0.69g 2-methylimidazole and add 30mL deionized water to make a solution, take 0.28g Zn(NO 3 ) 2 ⁇ 6H 2 O and add 30mL deionized water Make a solution, mix and stir for 10 minutes to obtain a mixed solution;
  • the maximum photocurrent measured by linear sweep voltammetry (LSV) of the ZnO/TiO 2 heterojunction composite photocatalyst was 0.96 mA/cm 2 (1.23 V vs RHE).

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Abstract

本发明属于复合材料技术领域，涉及光电催化剂的制备，尤其涉及一种MOF衍生的氧化锌复合二氧化钛(ZnO/TiO 2)异质结的制备方法，以六水合硝酸锌、钛酸四丁酯、2-甲基咪唑、浓盐酸和FTO玻璃片为原料，先利用简单快速的化学反应法得到FTO玻璃片表面负载TiO 2，再经吸附法和煅烧处理合成ZnO/TiO 2异质结。本发明还将所制得的ZnO/TiO 2异质结，应用于光电催化分解水制氢。Zn-MOF(ZIF-8)衍生的ZnO复合在TiO 2纳米棒表面，能够有效地增强ZnO/TiO 2异质结复合光电催化剂的载流子迁移速率，提升电子/空穴分离效率，增强催化剂对光的捕获能力，提高ZnO/TiO 2异质结的光电催化性能。本发明制备工艺较为简单，所制备的ZnO/TiO 2异质结在环境、能源等领域具有良好应用前景，特别是应用于光电催化分解水制氢。

Description

MOF衍生的氧化锌复合二氧化钛异质结的制备方法及光电分解水应用 技术领域
本发明属于复合材料制备技术领域，涉及光电催化剂的制备，尤其涉及一种MOF衍生的氧化锌复合二氧化钛(ZnO/TiO 2)异质结的制备方法及光电分解水应用。
背景技术
氢(H 2)作为一种具有高燃烧热值，可再生，无污染的新兴能源，受到广泛关注。在制氢的各种生产策略中，太阳能驱动的光电化学(PEC)分解水制氢是解决当前能源危机和环境问题的有效策略。但是，探索高效率的光电电极材料对于实际应用必不可少。在各种半导体材料中，TiO 2由于其结构稳定，含量丰富且价格低廉，被认为是有前途的PEC水分解光电电极材料。然而，高的电子/空穴复合率和缓慢的氧化反应动力学极大地限制了其光电性能。此外，TiO 2(金红石，3.0eV)具有较弱的光响应性能，无法有效利用太阳光谱。
构建异质结是有效的半导体改性方法。研究表明，TiO 2光电极和某些金属氧化物的组合是提高PEC性能的有效策略。选择合适的金属氧化物与TiO 2复合，形成的异质结构可以明显促进电子/空穴的分离，改善载流子迁移行为，并提高太阳光的利用率。Sun等人发现TiO 2和Fe 2O 3的组合可以显著改善PEC性能，利用水热法在TiO 2纳米棒上生长Fe 2O 3，Fe 2O 3的窄带隙可以增强光吸收，从而产生更多的光生载流子，有效促进PEC水的分解。在许多金属氧化物中，ZnO由于高电子迁移率和低载流子复合率而受到广泛关注。因此，它可以用作构建TiO 2异质结的有效候选材料。值得一提的是，ZnO和TiO 2的带隙能相似，因此构造的ZnO/TiO 2异质结构具有许多优点。Ng等人报道，ZnO复合在TiO 2纳米管上的，构造的异质结在光响应中产生明显的红移，从而扩大了可见光谱的响应范围。金属有机骨架(MOF)用作牺牲模板，通过煅烧生成金属氧化物，可以促进水分解。MOF为相应的金属氧化物提供特定的微观结构，而MOF衍生的金属氧化物材料可以保留MOF大的比表面积和多孔结构的特征，从而暴露出更多的活性位点，在增强水的分解过程中起着重要作用。
迄今为止，未见公开以Zn-MOF(ZIF-8)为前驱体，通过静电吸附法制备ZnO/TiO 2复合材料。
发明内容
为了解决TiO 2半导体材料电子空穴容易复合、仅能对紫外光响应，界面反应动力学缓慢的问题，本发明公开一种MOF衍生的氧化锌复合二氧化钛(ZnO/TiO 2)异质结的制备方法。
技术方案：
以钛酸四丁酯、浓盐酸、六水合硝酸锌(Zn(NO 3) 2·6H 2O)、2-甲基咪唑(C 4H 6N 2)、FTO玻璃片为原料，先利用简单快速的化学反应法得到FTO玻璃片表面负载TiO 2，再经吸附法和 煅烧处理合成ZnO/TiO 2异质结。
一种MOF衍生的氧化锌复合二氧化钛(ZnO/TiO 2)异质结的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：向3mol/L的HCl溶液中加入钛酸四丁酯，以体积比60:1～30:1混合搅拌均匀，优选50:1，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，150～200℃恒温5～10h，优选180℃恒温6h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉300～500℃煅烧1～4h，优选450℃煅烧2h制得负载有TiO 2的FTO片；
B、Zn-MOF(ZIF-8)前驱体溶液的制备：将2-甲基咪唑加入到Zn(NO 3) 2·6H 2O的去离子水溶液中，搅拌均匀得Zn-MOF(ZIF-8)溶液，其中，所述2-甲基咪唑、Zn(NO 3) 2·6H 2O和去离子水的质量体积比为0.5～0.8g:0.2～0.5g:60ml，优选0.66g:0.29g:60ml；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡1～16min后取出，用去离子水洗净，于300～500℃煅烧1～3h，优选350℃煅烧2h，得到氧化锌复合二氧化钛(ZnO/TiO 2)异质结。
本发明较优公开例中，步骤A中所述清洗干净的FTO玻璃片，先清洁FTO玻璃片表面，然后在丙酮、异丙醇和乙二醇中分别对其超声波清洗0.5h，取出，晾干。
根据本发明所公开的方法，制备得到的ZnO/TiO 2异质结，TiO 2纳米棒形貌均匀且规则，尺寸约为2～3μm，复合ZnO后TiO 2表面明显粗糙。
本发明的另一个目的是公开了将所制得的ZnO/TiO 2异质结，应用于光电催化分解水制氢。
光电催化分解水实验
(1)配制50mL浓度为0.5～1.5mol·L -1的NaOH溶液置于暗处，优选1mol·L -1并通入N 2持续30min；
(2)将不同浸泡时间处理过的ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
本发明的特点：
(1)引入ZnO形成ZnO/TiO 2异质结复合光电催化剂有效促进载流子迁移并且抑制电子空穴对复合；
(2)引入ZnO形成ZnO/TiO 2异质结复合光电催化剂使得光电催化制氢反应光响应范围拓展至可见光区。
本发明所制得的ZnO/TiO 2复合光电催化剂利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等仪器对产物进行形貌结构和组成分析，通过紫外-可见分光光度计测量吸光度，用标准的三电极电化学工作站测量瞬态光电流、稳定性，以评估其光电催化活性。
本发明所用反应物试剂，均为市售。
发明人通过静电吸附工艺制备ZnO/TiO 2异质结，经Zeta电位测试，TiO 2的Zeta电位为-31.98mV，而Zn-MOF(ZIF-8)的Zeta电位为39mV，因此通过静电吸附作用两者可以牢牢的结合在一起，进而可以进行热解处理将Zn-MOF(ZIF-8)转变为ZnO，从而制得ZnO/TiO 2复合光电催化剂。
有益效果
本发明利用水热法、浸泡法和煅烧处理合成ZnO/TiO 2异质结，Zn-MOF(ZIF-8)衍生的ZnO复合在TiO 2纳米棒表面，有效地增强ZnO/TiO 2异质结复合光电催化剂载流子迁移速率，提高电子空穴分离效率，增强了催化剂对光的捕获能力，提高了异质结复合光电催化剂的光电催化性能，所制备的ZnO/TiO 2催化剂在环境、能源等领域有良好应用前景，特别是应用于光电催化分解水制氢。
附图说明
图1.实施例1所制备ZnO/TiO 2复合光电催化剂的XRD衍射谱图；
图2.实施例1所制备ZnO/TiO 2复合光电催化剂的XPS图；
图3.实施例1所制备ZnO/TiO 2复合光电催化剂的扫描电子显微镜(SEM)图；
图4.实施例1所制备ZnO/TiO 2复合光电催化剂的UV-vis谱图；
图5.实施例1所制备ZnO/TiO 2复合光电催化剂的线性扫描伏安法(LSV)图；
图6.实施例1所制备ZnO/TiO 2复合光电催化剂的稳定性(I-t)图。
具体实施方式
下面结合实施例对本发明进行详细说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。
除非另外限定，这里所使用的术语(包含科技术语)应当解释为具有如本发明所属技术领域的技术人员所共同理解到的相同意义。还将理解到，这里所使用的术语应当解释为具有与它们在本说明书和相关技术的内容中的意义相一致的意义，并且不应当以理想化或过度的形式解释，除非这里特意地如此限定。
实施例1
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入1.2mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，180℃恒温6h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉450℃煅烧2h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.66g 2-甲基咪唑加入30mL去离子水配成溶液，取0.29g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得 混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，分别浸泡3、6、9分钟后取出，用去离子水冲洗，马弗炉350℃煅烧2h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为1mol·L -1的NaOH溶液置于暗处，并通入N 2持续30min；
(2)取不同浸泡时间的ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO /TiO 2异质结复合光电催化剂的表征
如图1所示，不同含量的ZnO/TiO 2异质结复合光电催化剂的XRD图谱显示，未发现ZnO的特征峰是由于ZnO含量低；
如图2所示，XPS图中包含Ti、O、Zn元素的存在且对应的价态，证明有效制备出ZnO；
如图3所示，TiO 2的纳米棒形貌以及ZnO均匀地附着在TiO 2表面；
如图4所示，纯TiO 2在410nm处表现出较窄的吸光率，ZnO/TiO 2异质结光电催化剂的吸光边则表现出明显的红移；
如图5所示，ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试在不同浸泡时间处理时的最大光电流1.76mA/cm 2(1.23V vs RHE)。
如图6所示，ZnO/TiO 2异质结复合光电催化剂具有良好的稳定性。
实施例2
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入1mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，200℃恒温7h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉400℃煅烧3h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.5g 2-甲基咪唑加入30mL去离子水配成溶液，取0.2g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡1、3、5分钟后取出，用去离子水冲洗，马弗炉300℃煅烧1h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为0.5mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.79mA/cm 2(1.23V vs RHE)。
实施例3
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入1.5mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，200℃恒温7h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉350℃煅烧2h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.55g 2-甲基咪唑加入30mL去离子水配成溶液，取0.25g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡2、4、6分钟后取出，用去离子水冲洗，马弗炉450℃煅烧2h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为0.8mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.87mA/cm 2(1.23V vs RHE)。
实施例4
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入2mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，150℃恒温10h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉500℃煅烧4h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.7g 2-甲基咪唑加入30mL去离子水配成溶液，取0.3g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡 5、10、15分钟后取出，用去离子水冲洗，马弗炉400℃煅烧2h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为1.5mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.53mA/cm 2(1.23V vs RHE)。
实施例5
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入1.5mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，170℃恒温7h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉420℃煅烧4h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.6g 2-甲基咪唑加入30mL去离子水配成溶液，取0.4g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡5、6、11分钟后取出，用去离子水冲洗，马弗炉380℃煅烧3h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为0.6mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.93mA/cm 2(1.23V vs RHE)。
实施例6
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入3mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，190℃恒温6h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉460℃煅烧3h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.8g 2-甲基咪唑加入30mL去离子水配成溶液，取0.5g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡7、10、16分钟后取出，用去离子水冲洗，马弗炉410℃煅烧2h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为0.8mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.67mA/cm 2(1.23V vs RHE)。
实施例7
一种Zn-MOF(ZIF-8)衍生的ZnO/TiO 2复合光电催化剂的制备方法，包括如下步骤：
A、TiO 2纳米棒阵列的制备：清洁FTO玻璃片，并在丙酮，异丙醇和乙二醇中分别对其进行超声波清洗0.5小时。配制摩尔浓度为3mol/L的HCl溶液，后向溶液中加入3mL的钛酸四丁酯，混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，190℃恒温6h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉480℃煅烧1h；
B、Zn-MOF(ZIF-8)前驱体的制备：取0.69g 2-甲基咪唑加入30mL去离子水配成溶液，取0.28g Zn(NO 3) 2·6H 2O加入30mL去离子水配成溶液，混合搅拌10分钟得混合溶液；
C、ZnO/TiO 2的制备：将负载有TiO 2的FTO片浸泡在Zn-MOF(ZIF-8)溶液中，浸泡8、9、10分钟后取出，用去离子水冲洗，马弗炉430℃煅烧1h，得到ZnO/TiO 2复合光电催化剂。
光电催化分解水实验
(1)配制50mL浓度为1.2mol·L -1的NaOH溶液置于暗处，并通入N 2持续30分钟；
(2)取ZnO/TiO 2样品，分别置于光电催化装置中，加入已配制的NaOH溶液，打开光源，进行光电催化分解水制氢实验。
ZnO/TiO 2异质结复合光电催化剂的线性扫描伏安法(LSV)测试的最大光电流0.96mA/cm 2(1.23V vs RHE)。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于，包括如下步骤：
    A.向3mol/L的HCl溶液中加入钛酸四丁酯，以体积比60:1～30:1混合搅拌均匀，将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，150～200℃恒温5～10h，自然冷却至室温取出并用去离子水洗涤、干燥，之后马弗炉300～500℃煅烧1～4h制得负载有TiO 2的FTO片；
    B.将2-甲基咪唑加入到Zn(NO 3) 2·6H 2O的去离子水溶液中，搅拌均匀得Zn-MOF溶液，其中所述2-甲基咪唑、Zn(NO 3) 2·6H 2O和去离子水的质量体积比为0.5～0.8g:0.2～0.5g:60ml；
    C.将负载有TiO 2的FTO片浸泡在Zn-MOF溶液中，浸泡1～16min后取出，用去离子水洗净，300～500℃煅烧1～3h，得到氧化锌复合二氧化钛ZnO/TiO 2异质结。
  2. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤A所述向3mol/L的HCl溶液中加入钛酸四丁酯，以体积比50:1混合搅拌均匀。
  3. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤A所述清洗干净的FTO玻璃片，先清洁FTO玻璃片表面，然后在丙酮、异丙醇和乙二醇中分别对其超声波清洗0.5h，取出，晾干。
  4. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤A所述将混合液转移到反应釜中，浸入清洗干净的FTO玻璃片，180℃恒温6h。
  5. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤A所述马弗炉450℃煅烧2h。
  6. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤B所述2-甲基咪唑、Zn(NO 3) 2·6H 2O和去离子水的质量体积比为0.66g:0.29g:60ml。
  7. 根据权利要求1所述MOF衍生的氧化锌复合二氧化钛异质结的制备方法，其特征在于：步骤C所述用去离子水洗净，350℃煅烧2h。
  8. 根据权利要求1-7任一所述方法制得的氧化锌复合二氧化钛ZnO/TiO 2异质结。
  9. 根据权利要求8所述的氧化锌复合二氧化钛ZnO/TiO 2异质结，其特征在于：TiO 2纳米棒形貌均匀且规则，尺寸约为2～3μm，复合ZnO后TiO 2表面明显粗糙。
  10. 一种如权利要求8或9所述氧化锌复合二氧化钛ZnO/TiO 2异质结的应用，其特征在于：将其应用于光电催化分解水制氢。
PCT/CN2022/078245 2021-01-04 2022-02-28 Mof衍生的氧化锌复合二氧化钛异质结的制备方法及光电分解水应用 WO2022144043A1 (zh)

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CN117658317A (zh) * 2023-12-06 2024-03-08 杭州绿能环保发电有限公司 一种低污泥产率的反硝化碳源及应用该碳源的垃圾渗滤液处理方法
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