阅读说明：本技术 一种铁掺杂钛氧簇材料及其合成方法与应用 (Iron-doped titanium-oxygen cluster material and synthesis method and application thereof ) 是由 王超 于 2020-07-20 设计创作，主要内容包括：本发明属于晶体材料制备技术领域,具体涉及一种铁掺杂钛氧簇材料及其合成方法与应用其合成方法与应用。所述铁掺杂钛氧簇的分子式Ti<Sub>2</Sub>Fe<Sub>4</Sub>(μ<Sub>3</Sub>-O)(μ<Sub>2</Sub>-O)(OOCPh)<Sub>12</Sub>(C<Sub>5</Sub>H<Sub>8</Sub>O<Sub>2</Sub>)(CH<Sub>3</Sub>CN)<Sub>4</Sub>,OOCPh为苯甲酸,μ<Sub>3</Sub>-O代表三连接的O原子,μ<Sub>2</Sub>-O代表二连接的O原子。合成步骤为：将钛酸异丙酯、乙酰丙酮铁、苯甲酸配体和乙腈溶剂加入反应釜中,室温下搅拌1~2h,于100~120℃条件下反应72~120h,降温,体系中析出晶体,分离、洗涤、干燥得到所述的铁掺杂钛氧簇。本发明制备得到的铁掺杂钛氧簇材料具有能量带隙窄、稳定性高、催化活性高等优势,在光降解有机污染物等方面具有广阔应用前景。(The invention belongs to the technical field of crystal material preparation, and particularly relates to an iron-doped titanium oxide cluster material, a synthesis method and application thereof. The molecular formula of the iron-doped titanium-oxygen cluster is Ti 2 Fe 4 (µ 3 ‑O)(µ 2 ‑O)(OOCPh) 12 (C 5 H 8 O 2 )(CH 3 CN) 4 OOCPh is benzoic acid, mu 3 O represents a triple bonded O atom,. mu. 2 -O represents a di-linked O atom. The synthesis steps are as follows: adding isopropyl titanate, iron acetylacetonate, a benzoic acid ligand and an acetonitrile solvent into a reaction kettle, stirring for 1-2 h at room temperature, reacting for 72-120 h at 100-120 ℃, cooling, separating out crystals in a system, separating, washing and drying to obtain the iron-doped titanyl cluster. The iron-doped titanium oxide cluster material prepared by the invention has the advantages of narrow energy band gap, high stability, high catalytic activity and the like, and has wide application prospect in the aspects of photodegradation of organic pollutants and the like.)

1. The iron-doped titanium oxide cluster material is characterized in that the molecular formula of the iron-doped titanium oxide cluster material is Ti₂Fe₄(µ₃-O)(µ₂-O)(OOCPh)₁₂(C₅H₈O₂)(CH₃CN)₄OOCPh is benzoic acid, C₅H₈O₂Is acetylacetone,. mu.₃O represents a triple bonded O atom,. mu.₂-O represents a di-linked O atom.

2. The iron-doped titanium oxide cluster material according to claim 1, wherein the iron-doped titanium oxide cluster material has a crystal structure of: the crystal belongs to a triclinic system and has a space group ofP-1The unit cell parameters are a =12.8825, b =13.6701 a, c =14.0873 a, α ═ 98.833 °, β ═ 92.963 °, γ ═ 117.785 °.

3. A method for synthesizing an iron-doped titanium-oxygen cluster material according to claim 1 or 2, comprising the steps of: adding isopropyl titanate, iron acetylacetonate, a benzoic acid ligand and an acetonitrile solvent into a reaction kettle, stirring for 0.5-1 h at room temperature, reacting for 48-96 h at 80-100 ℃, cooling to 25 ℃, separating out crystals in a system, separating, washing and drying to obtain the iron-doped titanyl cluster.

4. The synthesis method according to claim 3, wherein the mass-to-volume ratio of isopropyl titanate, ferric acetylacetonate, benzoic acid ligand and acetonitrile solvent is: (0.1-0.2) mL: (0.03-0.05) g: 0.1 g: (3-6) mL.

5. The synthesis method according to claim 3, wherein the temperature reduction is carried out in a program temperature control manner, and the temperature reduction rate is controlled to be 3-8 ℃/h.

6. The synthesis method according to claim 3, characterized in that the crystal is in an orange-red block shape; the washing is carried out for three times by adopting acetonitrile; the drying is natural drying.

7. Use of an iron-doped titanium oxide cluster material according to claim 1 or 2, for photo-degradation of organic contaminants.

Technical Field

The invention belongs to the technical field of crystal material preparation, and particularly relates to an iron-doped titanium-oxygen cluster material and a synthesis method and application thereof.

Background

Energy crisis and environmental pollution are two major challenges currently facing mankind, and the development of clean low-carbon new energy such as solar energy is imperative. The photocatalysis technology can directly convert solar energy into chemical energy, and the core of the technology is the synthesis of a stable and efficient photocatalyst. Nano titanium dioxide (TiO)₂) The material is considered as one of the most potential photocatalysts due to its characteristics of low cost, high efficiency and environmental friendliness. However, the nano-titania materials also have many non-negligible disadvantages, including unclear structural information, non-uniform particle size, inorganic-organicThe uncertain information of the machine interface, the uncertain surface composition and the like greatly hinder the intensive research on the photocatalytic materials.

In recent years, crystalline titanyl clusters have been used as nano TiO₂Molecular model compounds for material structure and performance are of great interest. However, because of the characteristics of high reactivity, easy hydrolysis and the like of a titanium source, the titanium clusters are reported less than other metal oxygen clusters, and even reported titanium cluster compounds have the problems of weak visible light absorption, wide energy band gap and the like, which severely limits the practical application of the titanium cluster compounds in photocatalysis. The metal dopant can change the electronic energy band structure and reduce the energy band gap thereof by introducing an additional energy level, thereby improving the photocatalytic activity of the titanium-oxygen cluster material and leading the material to have wide application prospect in the aspects of photocatalytic hydrogen production, photodegradation of organic pollutants and the like; at the same time, the nano TiO is doped with metal₂Molecular simulation and theoretical calculation of materials provide an excellent research platform. Therefore, the development of the metal doped titanium-oxygen cluster material has good economic benefit and social benefit.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides the iron-doped titanium oxide cluster material which has the advantages of strong visible light absorption, narrow energy band gap, high stability, high catalytic activity and the like, and has wide application prospect in the aspects of photodegradation of organic pollutants and the like.

The invention also aims to provide a synthesis method of the iron-doped titanium-oxygen cluster material, which has the characteristics of simple process, pure product, high yield, good crystallinity and the like.

In order to achieve the purpose, the invention adopts the technical scheme that:

the molecular formula of the iron-doped titanium oxide cluster material is Ti₂Fe₄(µ₃-O)(µ₂-O)(OOCPh)₁₂(C₅H₈O₂)(CH₃CN)₄OOCPh is benzoic acid, C₅H₈O₂Is acetylacetone,. mu.₃-O represents a triple-bonded O atom,μ₂-O represents a di-linked O atom.

Further, the crystal structure of the iron-doped titanium-oxygen cluster material is as follows: the crystal belongs to a triclinic system and has a space group ofP-1The unit cell parameters are a =13.39, b =13.88, c =23.92 a, α is 85.48 °, β is 83.20 °, γ is 81.27 °.

A synthetic method of the iron-doped titanium-oxygen cluster material comprises the following steps: adding isopropyl titanate, iron acetylacetonate, a benzoic acid ligand and an acetonitrile solvent into a reaction kettle, stirring for 0.5-1 h at room temperature, reacting for 48-96 h at 80-100 ℃, cooling to 25 ℃, separating out crystals in a system, separating, washing and drying to obtain the iron-doped titanium oxide cluster material.

Further, the mass-to-volume ratio of the isopropyl titanate, the ferric acetylacetonate, the benzoic acid ligand and the acetonitrile solvent is as follows: (0.1-0.2) mL: (0.03-0.05) g: 0.1 g: (3-6) mL.

Further, the temperature is reduced by adopting a program temperature control mode, and the temperature reduction rate is controlled to be 3-8 ℃/h.

Further, the washing is three times of washing with acetonitrile; the drying is natural drying; the crystals are in an orange-red block shape.

According to the application of the iron-doped titanyl cluster, the iron-doped titanyl cluster material can be applied to photodegradation of organic pollutants.

Advantageous effects

The iron-doped titanium oxide cluster material has the advantages of strong visible light absorption, narrow energy band gap, high stability, high catalytic activity and the like, and has wide application prospect in the aspects of photodegradation of organic pollutants and the like.

The synthesis method of the iron-doped titanium-oxygen cluster material has the characteristics of simple process, pure product, high yield, good crystallinity and the like.

Drawings

FIG. 1 is a graph of X-ray single crystal diffraction data for iron-doped titanyl clusters prepared in example 2;

FIG. 2 is a crystal photograph of an iron-doped titanyl cluster material prepared in example 2;

FIG. 3 is a structural diagram of an iron-doped titanium oxide cluster material prepared in example 2;

FIG. 4 is an X-ray powder diffraction pattern of the iron-doped titanium oxide cluster material prepared in example 2;

FIG. 5 is a thermogravimetric plot of the iron doped titanyl cluster material prepared in example 2;

fig. 6 is a uv-vis absorption spectrum of the iron-doped titanyl cluster material prepared in example 2.

Detailed Description

The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The raw materials and reagents used in the present invention are commercially available.

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples.