阅读说明：本技术 一种迅速升温制备二维局域氧化的过渡族金属氟化物催化剂方法 (It is a kind of to be brought rapidly up the magnesium-yttrium-transition metal fluoride-catalyzed agent method for preparing two-dimentional local oxidation ) 是由 黄凯 雷鸣 赵泽璧 于 2019-09-03 设计创作，主要内容包括：本发明涉及一种迅速升温制备二维局域氧化的过渡族金属氟化物催化剂方法,属于材料科学与工程技术和化学领域。本发明方法制备的氧化过渡族金属氟化物催化剂为氟化钴(CoF<Sub>2</Sub>)、氟化镍(NiF<Sub>2</Sub>)、氟化铁(FeF<Sub>3</Sub>)等纳米材料局域氧化。首先称量一定质量的水合氟化物作为原料A,通过迅速改变原料A所处的温度环境,从而制备出二维局域氧化的过渡族金属氟化物催化剂。本发明具有简单易行、高产量、高效率、适用性强等优点,相对于传统制备超薄二维纳米材料的方法具有显著的优势。(The present invention relates to a kind of magnesium-yttrium-transition metal fluoride-catalyzed agent methods for being brought rapidly up the two-dimentional local oxidation of preparation, belong to Materials Science and Engineering technology and chemical field.The oxidation magnesium-yttrium-transition metal fluoride catalysts of the method for the present invention preparation are cobaltous fluoride (CoF 2 ), nickel fluoride (NiF 2 ), ferric flouride (FeF 3 ) etc. nano materials local oxidation.The hydration fluoride of certain mass is weighed first as raw material A, by rapidly changing temperature environment locating for raw material A, to prepare the magnesium-yttrium-transition metal fluoride catalysts of two-dimentional local oxidation.The present invention has many advantages, such as simple and easy, high yield, high efficiency, strong applicability, and the method for preparing ultra-thin two-dimension nano material relative to tradition has significant advantage.)

1. a kind of be brought rapidly up the method for preparing the transition group metal catalyst of two-dimentional local oxidation, it is characterised in that this method packet Include following steps:

(1) suitable magnesium-yttrium-transition metal hydrate is chosen as raw material A, and weighs the raw material A of certain mass.The transition group gold Belonging to element is any one or more in Cr, Mn, Fe, Co, Ni, Cu and Zn, and the anion element is any in B, F, P One or more, the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃·4H₂O), it is hydrated manganous fluoride (MnF₂· 4H₂O), it is hydrated ferric flouride (FeF₃·3H₂O), it is hydrated cobaltous fluoride (CoF₂·4H₂O), it is hydrated nickel fluoride (NiF₂·4H₂O), it is hydrated Copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated cobalt (B₂CoF₈·6H₂O any in) It is one or more；

(2) raw material A for weighing above-mentioned steps (1), is put into rapidly in the complete Muffle furnace that heated up and heats, one timing of heating Between after rapidly take out reaction after sample, to sample be cooled to room temperature to sample carry out eccentric cleaning, local oxidation can be obtained Magnesium-yttrium-transition metal fluoride catalysts.The reaction atmosphere environment is air, and heating optional temperature range is 400 DEG C -500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heat optional time range be 10min-40min, as 10min, 15min, 20min, 40min。

(3) it chooses suitable magnesium-yttrium-transition metal hydrate to dissolve in water as raw material B, and by the raw material B of certain mass, be configured to Saturated solution C.The transiting group metal elements are any one or more in Cr, Mn, Fe, Co, Ni, Cu and Zn, the yin Ion elements are any one or more in B, F, P, and the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃· 4H₂O), it is hydrated manganous fluoride (MnF₂·4H₂O), it is hydrated ferric flouride (FeF₃·3H₂O), it is hydrated cobaltous fluoride (CoF₂·4H₂O), it is hydrated Nickel fluoride (NiF₂·4H₂O), it is hydrated copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated cobalt (B₂CoF₈·6H₂O any one or more in)；

(4) the saturated solution C for configuring above-mentioned steps (3), is put into rapidly in the complete Muffle furnace that heated up and heats, heating one The sample after reaction is taken out after fixing time rapidly, is cooled to room temperature to sample and eccentric cleaning is carried out to sample, local can be obtained The magnesium-yttrium-transition metal fluoride catalysts of oxidation.The reaction atmosphere environment be air, heat optional temperature range be 400 DEG C- 500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heat optional time range be 10min-40min, as 10min, 15min, 20min, 40min。

(5) suitable magnesium-yttrium-transition metal hydrate is chosen as raw material D, and micro ultrapure water is added to the raw material of certain mass Reactant E is made in D.The transiting group metal elements are any one or more in Cr, Mn, Fe, Co, Ni, Cu and Zn, institute Stating anion element is any one or more in B, F, P, and the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃· 4H₂O), it is hydrated manganous fluoride (MnF₂·4H₂O), it is hydrated ferric flouride (FeF₃·3H₂O), it is hydrated cobaltous fluoride (CoF₂·4H₂O), it is hydrated Nickel fluoride (NiF₂·4H₂O), it is hydrated copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated cobalt (B₂CoF₈·6H₂O any one or more in)；

(6) the reactant E for configuring above-mentioned steps (5), is put into rapidly in the complete Muffle furnace that heated up and heats, and heating is certain The sample after reaction is taken out after time rapidly, is cooled to room temperature to sample and eccentric cleaning is carried out to sample, local oxygen can be obtained The magnesium-yttrium-transition metal fluoride catalysts of change.The reaction atmosphere environment is air, and heating optional temperature range is 400 DEG C -500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heat optional time range be 10min-40min, as 10min, 15min, 20min, 40min。

(2) technical field

The present invention relates to the method for preparing the magnesium-yttrium-transition metal fluoride catalysts of two-dimentional local oxidation is brought rapidly up, belong to Materials Science and Engineering technology and chemical field.

(3) background technique

So far, scientist is it has been reported that a variety of methods for preparing two-dimension nano materials.It is used to prepare two-dimensional nano The most common strategy of material first is that mechanically or chemically removing some stratified materials, such as BN, MoS₂, MoSe₂, MoTe₂And TaSe, These materials are easy to the side in face with Van der Waals interaction outside chemical bond in strong face and weak face under extreme conditions It removes downward vertically.The preparation of MXene is then by from MAX phase solid (such as Ti in two-dimension nano materials₃AlC₂) in selectivity Etch A race atom.Many two-dimensional metallic oxide-based nanomaterials, such as TiO₂, Zn and MnO₂Self assembly or other humidifyings can be passed through Method manufacture.The two-dimension nano materials of some not layered crystal structures can also be synthesized by metal ion solution.Example Such as, researcher passes through solvent heat and wet chemical method respectively and is prepared for super thin metal two-dimensional nano material from the materials such as rhodium and gold Material.Although the method that researcher has studied many synthesis two-dimensional materials, these methods are usually very complicated, expensive and effect Rate is low.The chemically or physically method for lacking a large amount of synthesis ultrathin nanometer materials limits the further exploitation of these two-dimensional materials And application.Therefore, for the simple of two-dimension nano materials to be mass produced, quickly and economic method is still one interesting Challenge.

In liquid stripping means, lewis' acid is usually in intercalation, to weaken Van der Waals interaction outside layer, so Exfoliation layer structural material afterwards.There is also some similar layer structure mineral in nature, molecule between layers, Such as vermiculite.Vermiculite is by the clay of laminar silicate mineral composition of one group of 2:1, these clay minerals are by aqueous sheet silicate Composition contains multilayer hydrone inside it in structure.When heated, since interlayer generates steam, cause vermiculite to have and do not seek Normal expansion characteristics (commercial variety can expand 8-20 times or more).Therefore, when mineral are sufficiently heated, it may occur that thin leech The peeling of rock layers.The inspiration for expanding and peeling off when being heated by vermiculite, we carry out the place that is rapidly heated to hydration fluoride Reason.In this way, we successfully obtain ultrathin nanometer grade stratified material, it is important that pass through this Fast Process It can produce a large amount of two-dimension nano materials.That is, present invention firstly provides and realize and be brought rapidly up volume production two dimension mistake Cross metal catalized dose of race.

(4) summary of the invention

1, target of the invention

The purpose of the present invention is to propose to one kind to be brought rapidly up the two-dimentional local oxidation magnesium-yttrium-transition metal fluoride catalysts of preparation Method, it is simple, prepare effectively and on a large scale the magnesium-yttrium-transition metal fluorine of two-dimentional local oxidation using rapidly changing environment temperature Compound catalyst, to significantly reduce the cost of transition group metal catalyst large-scale commercial application.

2, the invention main points of this technology

Main points of the present invention are as follows:

(1) suitable magnesium-yttrium-transition metal hydrate is chosen as raw material A, and weighs the raw material A of certain mass.The transition Race's metallic element is any one or more in Cr, Mn, Fe, Co, Ni, Cu and Zn, and the anion element is in B, F, P Any one or more, the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃·4H₂O), it is hydrated manganous fluoride (MnF₂· 4H₂O), it is hydrated ferric flouride (FeF₃· 3H₂O), it is hydrated cobaltous fluoride (CoF₂·4H₂O), it is hydrated nickel fluoride (NiF₂·4H₂O), water Close copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated cobalt (B₂CoF₈· 6H₂Appointing in O) It anticipates one or more；

(2) raw material A for weighing above-mentioned steps (1), is put into rapidly in the complete Muffle furnace that heated up and heats, heating one The sample after reaction is taken out after fixing time rapidly, is cooled to room temperature to sample and eccentric cleaning is carried out to sample, local can be obtained The magnesium-yttrium-transition metal fluoride catalysts of oxidation.The reaction atmosphere environment be air, heat optional temperature range be 400 DEG C- 500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heat optional time range be 10min-40min, as 10min, 15min, 20min, 40min。

(3) it chooses suitable magnesium-yttrium-transition metal hydrate to dissolve in water as raw material B, and by the raw material B of certain mass, match It is set to saturated solution C.The transiting group metal elements are any one or more in Cr, Mn, Fe, Co, Ni, Cu and Zn, institute Stating anion element is any one or more in B, F, P, and the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃· 4H₂O), it is hydrated manganous fluoride (MnF₂· 4H₂O), it is hydrated ferric flouride (FeF₃·3H₂O), it is hydrated cobaltous fluoride (CoF₂·4H₂O), water Close nickel fluoride (NiF₂·4H₂O), it is hydrated copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated tetrafluoro boric acid Cobalt (B₂CoF₈·6H₂O any one or more in)；

(4) the saturated solution C for configuring above-mentioned steps (3), is put into rapidly in the complete Muffle furnace that heated up and heats, add Heat takes out rapidly the sample after reaction after a certain period of time, is cooled to room temperature to sample and carries out eccentric cleaning to sample, can be obtained The magnesium-yttrium-transition metal fluoride catalysts of local oxidation.The reaction atmosphere environment is air, and heating optional temperature range is 400 DEG C -500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heating optional time range is 10min-40min, as 10min, 15min, 20min、40min。

(5) it chooses suitable magnesium-yttrium-transition metal hydrate and certain mass is added as raw material D, and by micro ultrapure water Reactant E is made in raw material D.The transiting group metal elements be Cr, Mn, Fe, Co, Ni, Cu and Zn in any one or it is more Kind, the anion element is any one or more in B, F, P, and the magnesium-yttrium-transition metal hydrate is hydration charomic fluoride (CrF₃·4H₂O), it is hydrated manganous fluoride (MnF₂· 4H₂O), it is hydrated ferric flouride (FeF₃·3H₂O), it is hydrated cobaltous fluoride (CoF₂· 4H₂O), it is hydrated nickel fluoride (NiF₂·4H₂O), it is hydrated copper fluoride (CuF₂·2H₂O), it is hydrated zinc fluoride (ZnF₂·4H₂O), it is hydrated Cobalt (B₂CoF₈·6H₂O any one or more in)；

(6) the reactant E for configuring above-mentioned steps (5), is put into rapidly in the complete Muffle furnace that heated up and heats, and heats It takes out the sample after reaction rapidly after a certain period of time, is cooled to room temperature to sample and eccentric cleaning is carried out to sample, office can be obtained The magnesium-yttrium-transition metal fluoride catalysts of domain oxidation.The reaction atmosphere environment is air, and heating optional temperature range is 400 DEG C -500 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, heating optional time range is 10min-40min, as 10min, 15min, 20min、40min。

The method proposed by the present invention for being brought rapidly up preparation oxidation magnesium-yttrium-transition metal fluoride catalysts, the advantage is that energy Enough simple, efficiently mass production two-dimension nano materials.Suitable for a variety of transiting group metal elements materials, as Cr, Mn, Fe, Co, Ni, Cu and Zn, while being suitable for adulterating one or more anion, such as B, F, P.

(5) attached drawing of the invention

Fig. 1 is the scanning transmission electron microscope of the cobaltous fluoride two-dimension nano materials of the local oxidation of the method for the present invention preparation Figure.

Fig. 2 be the method for the present invention preparation local oxidation cobaltous fluoride two-dimension nano materials oxygen be precipitated electro catalytic activity with Stability test performance map.(a), (b) and (c) is followed successively by polarization curve under nitrogen saturation conditions in 1M KOH electrolyte, steady Qualitative curve and Tafel kinetic curve；(d) bent for the long-time stability in 1M KOH electrolyte under nitrogen saturation conditions Line.

(6) embodiment of the present invention

The embodiment of the method for the present invention introduced below:

Embodiment 1

The preparation of the cobaltous fluoride two-dimension nano materials of local oxidation.

Firstly, weighing raw material A: 300mg CoF₂·4H₂Raw material A is put into rapidly in 400 DEG C of Muffle furnace and keeps the temperature by O Then 20min takes out rapidly the sample after reaction, clear by way of being centrifuged repeatedly cleaning after making its cooled to room temperature Sample is washed, after vacuum drying, can be obtained the cobaltous fluoride two-dimension nano materials of local oxidation.Wherein each centrifugation rate is 10000 turns, centrifugation time 10min.