阅读说明：本技术 含有Sn-Sb-过渡金属元素的活性材料、制备方法以及含有该活性材料的臭氧发生电极 (Active material containing Sn-Sb-transition metal element, preparation method and ozone generating electrode containing active material ) 是由 宋兴余 李富昌 于 2018-06-05 设计创作，主要内容包括：本发明涉及含有Sn-Sb-过渡金属元素的活性材料、制备方法以及含有该活性材料的臭氧发生电极。所述活性材料中,Sn元素、Sb元素、过渡金属元素的质量占比为：200～900：3～8：0.1～4,其中,所述过渡金属元素为第一过渡系元素和第二过渡系元素；所述Sn元素取自含正二价Sn的化合物,所述Sb元素取自含正三价Sb的化合物,所述过渡金属元素取自含稳定价态过渡金属元素的化合物。本发明制备的活性材料易于储存,制备工艺简便,易操作,且可作为制备臭氧过程的催化剂。(The present invention relates to an active material containing an Sn-Sb-transition metal element, a method for producing the same, and an ozone generating electrode containing the active material. In the active material, the mass ratio of Sn element, Sb element and transition metal element is as follows: 200-900: 3-8: 0.1 to 4, wherein the transition metal element is a first transition element and a second transition element; the Sn element is taken from a compound containing bivalent Sn, the Sb element is taken from a compound containing trivalent Sb, and the transition metal element is taken from a compound containing a transition metal element with a stable valence state. The active material prepared by the method is easy to store, the preparation process is simple and convenient, the operation is easy, and the active material can be used as a catalyst in the process of preparing ozone.)

1. The active material containing the Sn-Sb-transition metal element is characterized in that the mass ratio of the Sn element to the Sb element to the transition metal element in the active material is as follows: 200-900: 3-8: 0.1 to 4, wherein the transition metal element is a first transition element and a second transition element; the Sn element is taken from a compound containing bivalent Sn, the Sb element is taken from a compound containing trivalent Sb, and the transition metal element is taken from a compound containing a transition metal element with a stable valence state.

2. The active material according to claim 1, wherein the mass ratio of the Sn element to the Sb element to the transition metal element is as follows: 280-870: 4-7: 0.2 to 3.

3. The active material of claim 1, wherein the compound containing the Sn element is SnC₂O₄(ii) a The compound containing the Sb element is Sb₂O₃(ii) a The transition metal elementThe element is one of Cr element, Co element, Nb element and Ru element.

4. The active material according to claim 3, wherein the compound containing the transition metal element is CoC₂O₄·2H₂O、Co(CH₃COO)₂·4H₂O、Cr(CH₃COO)₃·2H₂O、Cr₂(C₂O₄)₃·6H₂O、Ru(CH₃COO)₃、Nb(HC₂O₄)₅One kind of (1).

5. A method for producing an active material containing an Sn-Sb-transition metal element according to any one of claims 1 to 4, characterized in that the method for producing the active material comprises the steps of:

A. 500-1500 parts by weight of SnC₂O₄Placing the mixture into a reaction kettle, adding at least 150 parts by weight of water into the reaction kettle for stirring, and then adding 5-8 parts by weight of Sb₂O₃Adding the mixture into the reaction kettle, stirring and heating the mixture to uniformly mix the mixture to obtain turbid liquid;

B. Adding a transition metal element compound containing the transition metal element into the turbid liquid, uniformly stirring, introducing oxygen into the reaction kettle, stirring, and stopping heating until the material in the reaction kettle is in a suspended state, wherein the weight of the transition metal element in the transition metal element compound is 0.1-4 parts by weight;

C. And D, taking the reaction kettle in the step B, cooling the reaction kettle, completely precipitating, and taking the upper suspension to obtain the active material.

6. The method according to claim 5, wherein in the step B, 1 to 3 parts by weight of CoC is added to the turbid liquid₂O₄·2H₂O; or adding 2-7 parts by weight of Co (CH) into the turbid solution₃COO)₂·4H₂O。

7. The method according to claim 5, wherein 1.5 to 5 parts by weight of Cr (CH) is added to the turbid liquid in the step B₃COO)₃·2H₂O; or adding 3-8 parts by weight of Cr into the turbid liquid₂(C₂O₄)₃·6H₂O。

8. The method according to claim 5, wherein in the step B, 4 to 7 parts by weight of Ru (CH) is added to the turbid liquid₃COO)₃。

9. The method according to claim 5, wherein in the step B, 5.5 to 15 parts by weight of Nb (HC) is added to the turbid solution₂O₄)₅。

10. An ozone generating electrode, characterized in that the ozone generating electrode is prepared by the following method:

1) taking the active material containing Sn-Sb-transition metal element as claimed in any one of claims 1 to 4, uniformly coating the active material on an electrode plate, and then performing pyrolysis at the temperature of 350-800 ℃;

2) Repeating the process of the step 1) for 8-20 times.

Technical Field

The invention relates to the field of chemical materials, in particular to an active material containing Sn-Sb-transition metal elements, a method for preparing the active material and an ozone generating electrode containing the active material.

background

Ozone O₃Also called superoxide, belonging to oxygen O₂The allotrope of (a). At normal temperature, the half-life period of ozone is 15-30 min (minutes), so that the conventional storage of ozone is difficult and the cost is high. Meanwhile, the ozone has strong oxidizability and easy decomposability, and can be used as a sewage purifying agent, a decolorizing agent, a disinfectant and the like. The ozone sterilization and disinfection speed is high, the effect is good, and the ozone is reduced to generate oxygen. Therefore, the use of ozone has been widely recognized and is a world recognized green disinfectant.

At present, the common methods for producing ozone include corona method, electrolytic method, ultraviolet method and nuclear radiation method. Wherein, the equipment investment of the corona method is higher, the running cost is high, and the concentration of the produced ozone is low; the ultraviolet method has high energy consumption and low concentration of generated ozone, and is not suitable for the production of a large amount of ozone; the nuclear radiation method has large investment, is unsafe and has low use frequency.

The production of ozone by electrolysis mainly comprises the steps of electrolyzing air and electrolyzing pure water. The process of electrolyzing air to produce ozone generates NO_xThe required alternating voltage is higher, the electrolysis efficiency is low, ozone is difficult to enter water, the occupied area of equipment is large, and the use cost is extremely high; the efficiency of ozone generated by electrolyzing pure water unit is highest, the electrolysis process takes solid noble metal polymer as electrolyte, combines with cation exchange mode, and obtains ozone by low-pressure electrolysis, but in the process, the control system is complex, the electrolysis efficiency is low, the ozone is difficult to enter water, and the use cost is high.

Therefore, the preparation and application of ozone have received wide attention from scholars at home and abroad.

The transition metal has the characteristics of high melting point, high boiling point, high hardness and high density, and has metallic luster, good ductility, good electrical conductivity and good thermal conductivity. Further, there may be a single d electron in an atom or ion of the transition metal element, and the spin of the electron determines the magnetic properties of the atom or molecule. Resulting in paramagnetism in many transition metals, which are useful as magnetic materials. The empty d orbitals for bonding in the transition elements and the high charge/radius ratio easily form stable coordination compounds with various ligands. The transition metal element has wide application in the field of material preparation.

Disclosure of Invention

In view of the above problems, the present invention is directed to providing an active material containing a transition metal element, which can be coated on an electrode plate for generating ozone during electrolysis.

One of the purposes of the invention is to provide an active material containing Sn-Sb-transition metal elements, wherein the mass ratio of the Sn elements, the Sb elements and the transition metal elements in the active material is as follows: 200-900: 3-8: 0.1 to 4, wherein the transition metal element is a first transition element and a second transition element; the Sn element is taken from a compound containing bivalent Sn, the Sb element is taken from a compound containing trivalent Sb, and the transition metal element is taken from a compound containing a transition metal element with a stable valence state.

in a preferred embodiment of the present invention, the mass ratio of the Sn element, the Sb element, and the transition metal element is: 280-870: 4-7: 0.2 to 3.

In a preferred embodiment of the present invention, the compound containing Sn is SnC₂O₄(ii) a The compound containing the Sb element is Sb₂O₃(ii) a The transition metal element is one of Cr element, Co element, Nb element and Ru element.

Further, the compound containing the transition metal element is CoC₂O₄·2H₂O、Co(CH₃COO)₂·4H₂O、Cr(CH₃COO)₃·2H₂O、Cr₂(C₂O₄)₃·6H₂O、Ru(CH₃COO)₃、Nb(HC₂O₄)₅One kind of (1).

It is another object of the present invention to provide a method for preparing the above active material, comprising the steps of:

A. 500-1500 parts by weight of SnC₂O₄Placing the mixture into a reaction kettle, adding at least 150 parts by weight of water into the reaction kettle, and stirringThen 5-8 parts by weight of Sb₂O₃Adding the mixture into the reaction kettle, stirring and heating the mixture to uniformly mix the mixture to obtain turbid liquid;

B. Adding a transition metal element compound containing the transition metal element into the turbid liquid, uniformly stirring, introducing oxygen into the reaction kettle, stirring, and stopping heating until the material in the reaction kettle is in a suspended state, wherein the weight of the transition metal element in the transition metal element compound is 0.1-4 parts by weight;

C. And D, taking the reaction kettle in the step B, cooling the reaction kettle, completely precipitating, and taking the upper suspension to obtain the active material.

In a preferred embodiment of the present invention, in the step B, 1 to 3 parts by weight of CoC is added to the turbid solution₂O₄·2H₂O; or adding 2-7 parts by weight of Co (CH) into the turbid solution₃COO)₂·4H₂O。

In a preferred embodiment of the present invention, in the step B, 1.5 to 5 parts by weight of Cr (CH) is added to the turbid liquid₃COO)₃·2H₂O; or adding 3-8 parts by weight of Cr into the turbid liquid₂(C₂O₄)₃·6H₂O。

In a preferred embodiment of the present invention, in the step B, 4 to 7 parts by weight of Ru (CH) is added to the turbid solution₃COO)₃。

In a preferred embodiment of the present invention, in the step B, 5.5 to 15 parts by weight of Nb (HC) is added to the turbid solution₂O₄)₅。

The invention also provides an ozone generating electrode, which is prepared by the following method:

1) Uniformly coating the active material containing the Sn-Sb-transition metal element on an electrode plate, and then carrying out pyrolysis at the temperature of 350-800 ℃;

2) Repeating the process of the step 1) for 8-20 times.

the active material containing the Sn-Sb-transition metal element is prepared by a specific process, the preparation process is simple and easy to operate, and the prepared active material is stable in property and convenient to store.

Furthermore, the active material containing Sn-Sb-transition metal elements prepared by the invention can be used as a catalyst for the process of generating ozone by electrolysis. The active material is coated on a proper electrode plate and is pyrolyzed and sintered, so that a uniform catalyst film layer is formed on the electrode plate. The electrode plate coated with the active material is used as the anode of the electrolysis device, and the water is electrolyzed to generate ozone under proper electrolysis conditions, so that the problem of difficult storage of the ozone is effectively solved. In addition, the ozone generated by electrolysis can directly act on the polluted water body to be treated, so that the water inlet rate of the ozone is greatly improved, and the treatment efficiency is improved.

Drawings

FIG. 1 is a schematic flow chart of the method for preparing Co-doped active material according to the present invention.

FIG. 2 is a schematic flow chart of the method for preparing the Cr-doped active material according to the present invention.

Fig. 3 is a schematic flow chart of a method for preparing a Ru-doped active material according to the present invention.

Fig. 4 is a schematic flow chart of a method for preparing an Nb-doped active material according to the present invention.

Detailed Description

The following detailed description of the present invention, taken in conjunction with the accompanying drawings and examples, is provided to enable the invention and its various aspects and advantages to be better understood. However, the specific embodiments and examples described below are for illustrative purposes only and are not limiting of the invention.

It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.

Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Firstly, the invention provides an active material containing Sn-Sb-transition metal elements. The active material of the invention contains Sn element, Sb element and transition metal element in the following mass ratio: 200-900: 3-8: 0.1 to 4. Preferably, in a different embodiment of the present invention, the mass ratio of the Sn element, the Sb element, and the transition metal element is: 280-870: 4-7: 0.2 to 3.

The Sn element contained in the active material of the present invention is a compound containing divalent and positive Sn. Preferably, the Sn-containing compound is SnC₂O₄. The Sb element contained in the active material is taken from a compound containing trivalent positive Sb. Preferably, the Sb element-containing compound is Sb₂O₃。

In the active material of the present invention, the transition metal element is selected from the group consisting of a first transition element and a second transition element. In a preferred embodiment of the present invention, the transition metal element is one selected from the group consisting of a Cr element, a Co element, a Nb element, and a Ru element.

Further, the transition metal element contained in the active material of the present invention is taken from a compound containing a transition metal element in a stable valence state. Preferably, the compound containing a transition metal element in a stable valence state is selected from CoC₂O₄·2H₂O、Co(CH₃COO)₂·4H₂O、Cr(CH₃COO)₃·2H₂O、Cr₂(C₂O₄)₃·6H₂O、Ru(CH₃COO)₃、Nb(HC₂O₄)₅One kind of (1).

The inventor finds that when oxalate series or acetate series is selected as the doped transition metal element in the active material of the invention, the interference of other impurity ions can be effectively avoided, thereby ensuring the purity of the active material.

Meanwhile, the invention also provides a preparation method of the active material containing the Sn-Sb-transition metal element. The preparation method comprises the following steps:

A. 500-1500 parts by weight of SnC₂O₄Placing the mixture into a reaction kettle, adding at least 150 parts by weight of water into the reaction kettle for stirring, and then adding 5-8 parts by weight of Sb₂O₃adding the mixture into a reaction kettle, stirring and heating the mixture to uniformly mix the mixture to obtain turbid liquid.

B. Adding a transition metal element compound containing a transition metal element into the turbid liquid, uniformly stirring, introducing oxygen into the reaction kettle, stirring, and stopping heating until the materials in the reaction kettle are in a suspension state. Wherein, in the transition metal element compound, the weight of the transition metal element is controlled to be 0.1-4 parts by weight.

C. And D, cooling the reaction kettle in the step B, completely precipitating, and taking the upper suspension to obtain the active material.

as a preferred embodiment of the present invention, SnC added in step A₂O₄Controlled to 600-870 weight portions. Preferably, the amount of water added is 150 to 450 parts by weight, and the mass of water added is not limited in various embodiments of the present invention, and the water added should be at least SnC₂O₄And (4) submerging. More preferably, deionized water is added to the reaction kettle.

in the step A, the time of the stirring process is preferably controlled to be 3-5 min. Adding Sb into a reaction kettle₂O₃Then, slowly heating the reaction kettle to 50-60 ℃ to ensure that SnC₂O₄and Sb₂O₃Mixing well to obtain turbid solution.

In the different embodiment of the present invention, preferably, in the step B, 1 to 3 parts by weight of CoC is added to the turbid liquid₂O₄·2H₂O；

Or adding 2-7 parts by weight of Co (CH) into the turbid solution₃COO)₂·4H₂O；

Or adding 1.5-5 parts by weight of Cr (CH) into the turbid solution₃COO)₃·2H₂O；

Or adding 3-8 parts by weight of Cr into the turbid liquid₂(C₂O₄)₃·6H₂O；

Or adding 4-7 parts by weight of Ru (CH) into the turbid solution₃COO)₃；

Or, adding 5.5-15 weight parts of Nb (HC) into the turbid solution₂O₄)₅。

According to different production requirements, different transition metal element compounds can be selected, and the amount of the added transition metal element is selected according to the requirements of the production process. Preferably, when the doped transition metal element is oxalate compound or acetate compound, the interference of other impurity ions can be effectively avoided, so that the purity of the active material is ensured.

And introducing oxygen into the reaction kettle at a flow rate of 7-14L/min. And C, in the reaction process of the step B, controlling the temperature in the reaction kettle to be maintained at 50-60 ℃, wherein energy waste is caused by overhigh temperature, and the reaction can not be fully carried out due to overlow temperature.

In the invention, the heating time is not limited, and can be selected according to actual needs. In the invention, the heating time is preferably controlled to be 1-2 h.

In various embodiments of the present invention, a certain amount of absolute alcohol is first added to the turbid liquid before the transition metal compound is added to the turbid liquid to increase the dispersibility of the transition metal compound in the turbid liquid.

In the step C, the time for naturally cooling and precipitating the reaction kettle is 5-7 hours.

Finally, the invention provides an ozone generating electrode. The ozone generating electrode is an electrode with a catalyst film layer covered on the surface, which is obtained by uniformly coating the active material containing Sn-Sb-transition metal elements on an electrode plate and then carrying out pyrolysis sintering.

The ozone generating electrode of the present invention is prepared by the following method:

1) The active material containing Sn-Sb-transition metal elements prepared by the method is uniformly coated on an electrode plate, and then is pyrolyzed at the temperature of 350-800 ℃. Preferably, the pyrolysis temperature is controlled to be 450-600 ℃.

2) Repeating the process of the step 1) for 8-20 times to enable the electrode plate to be uniformly covered with the film layer, wherein the film layer formed by pyrolysis sintering can be used as a catalyst for generating ozone in the water electrolysis process of the electrode plate, and the ozone generating electrode is obtained. Preferably, the process of the step 1) is repeated for 12 to 16 times.

In various embodiments of the present invention, the electrode plate may be made of a metal conductive material, such as a titanium plate, a platinum metal plate, or the like. Alternatively, the electrode plate may be made of a non-metallic conductive material, such as conductive ceramic or conductive silicon.

The ozone generating electrode prepared by the invention can be used as an anode of an electrolysis device, and can be used for treating polluted water under proper electrolysis conditions. In the electrolysis process, the ozone generating electrode is used as an anode to electrolyze water to generate a large amount of ozone, and the generated ozone directly acts on polluted water to realize pollution treatment. Moreover, no toxic and harmful substances are generated in the pollution treatment process, the treatment efficiency is high, and the operation is simple and convenient.

in different embodiments of the invention, the ozone generating electrode can also be used for treating pollution in other fields.