阅读说明：本技术 一种Cu2O纳微晶体及其制备方法、应用 (A kind of Cu2O receive microcrystal and preparation method thereof, application ) 是由 张新民 刘丹 朱辉 郑陈彪 蔡志炬 何凤荣 于 2019-08-29 设计创作，主要内容包括：本发明涉及一种Cu_2O纳微晶体及其制备方法、应用。制备方法为：将铜的可溶性盐的溶液加热至55～70℃,加入碱溶液,生成沉淀,然后加入还原剂进行还原反应,之后离心、干燥,得到Cu_2O纳微晶体；其中,所述碱溶液为NaOH水溶液和KOH水溶液中的至少一种,所述铜的可溶性盐的溶液所用的溶剂为水和乙醇中的至少一种,优选至少含有水；所述还原剂为抗坏血酸和盐酸羟胺的混合物。本发明能够制得直径在1.0μm以下的Cu_2O多面体,并且能制备出形貌产率大于95％的具有衍射指数晶面{311}的Cu_2O五十面体。(The present invention relates to a kind of Cu 2 O receive microcrystal and preparation method thereof, application.The preparation method comprises the following steps: the solution of the soluble-salt of copper is heated to 55~70 DEG C, aqueous slkali is added, generates precipitating, reducing agent is then added and carries out reduction reaction, is centrifuged later, is dry, obtaining Cu 2 O receives microcrystal；Wherein, the aqueous slkali is at least one of NaOH aqueous solution and KOH aqueous solution, and solvent used in the solution of the soluble-salt of the copper is at least one of water and ethyl alcohol, preferably at least contains water；The reducing agent is the mixture of ascorbic acid and hydroxylamine hydrochloride.Diameter can be made in 1.0 μm of Cu below in the present invention 2 O polyhedron, and the Cu with indices of diffraction crystal face { 311 } that pattern yield is greater than 95% can be prepared 2 Five decahedron of O.)

1. a kind of Cu₂O receives the preparation method of microcrystal, characterized in that it comprises the following steps:

The solution of the soluble-salt of copper is heated to 55~70 DEG C, aqueous slkali is added, generates precipitating, reducing agent is then added and carries out Reduction reaction is centrifuged later, is dry, obtaining Cu₂O receives microcrystal；

Wherein, the aqueous slkali is at least one of NaOH aqueous solution and KOH aqueous solution；

Solvent used in the solution of the soluble-salt of the copper is at least one of water and ethyl alcohol, preferably at least contains water；

The reducing agent is the mixture of ascorbic acid and hydroxylamine hydrochloride.

2. preparation method according to claim 1, which is characterized in that the soluble-salt of the copper is nitrate, the chlorine of copper One or more of salt dissolving, acetate.

3. preparation method according to claim 1 or 2, which is characterized in that used in the solution of the soluble-salt of the copper Solvent are as follows: water and ethyl alcohol are formed with 14:1~10:1 volume ratio.

4. preparation method according to claim 1 or 2, which is characterized in that the concentration of the solution of the soluble-salt of the copper For 1.0~1.2 μm of ol/mL.

5. preparation method according to claim 1 or 2, which is characterized in that the concentration of the aqueous slkali be 5.0~ 12.0mol/L, preferably 8.0~10.0mol/L.

6. preparation method according to claim 1, which is characterized in that after generation precipitating and the addition reducing agent Continue 3~5min of stirring before.

7. preparation method according to claim 1, which is characterized in that the reducing agent is added as an aqueous solution, anti-bad The concentration of hematic acid aqueous solution and hydroxylamine hydrochloride aqueous solution is all 0.02-0.5mol/L, and the total concentration of reducing agent aqueous solution is preferably 0.1-0.2mol/L。

8. preparation method according to claim 7, which is characterized in that the aqueous ascorbic acid and hydroxylamine hydrochloride are water-soluble The volume ratio of liquid is 1~5:5~1.

9. preparation method according to claim 1 or claim 7, which is characterized in that the time of the reduction reaction be 10~ 60min。

10. using Cu made from the described in any item preparation methods of claim 1-9₂O receives microcrystal.

11. Cu according to claim 10₂O receives microcrystal, includes at least with five decahedrons of flowering structure: by square, Five decahedrons that trapezoidal and two kinds of hexagons are formed by total side connection type, wherein each square and four trapezoidal connections, It is each trapezoidal to be connect with a square and three hexagons.

12. Cu described in claim 10 or 11₂O receives the application of microcrystal, the Cu₂O receives microcrystal for making semiconductor device Part or catalysis Ullmann reaction, preferably heterocatalysis Ullmann reaction, the C-N or C-O of preferred catalytic Ullmann type intersect even Connection reaction.

Technical field

The present invention relates to crystal material field, in particular to a kind of Cu₂O receive microcrystal and preparation method thereof, application.

Background technique

Carbon-to-carbon (C-C), carbon-hetero atom (C-R) (R includes oxygen, nitrogen, sulphur, phosphorus, selenium etc.) key between aryl and aryl Formation is a kind of very important means in modern organic synthesis.This kind of chemical bonding structure is typically found in natural products, biology Alkali (such as vancomycin, Chloropeptins) or it is some have physiological activity drug (such as TA- I-IV, OF4949- I-IV, Piperazinomycin, K-13) etc. compound in.It is artificial synthesized to trace back to what Fritz Ullmann in 1901 was reported Halogenated aryl hydrocarbon heats in the presence of copper powder and undergoes coupling reaction to produce biphenyl compound.Synthetic product such as diaryl ethers and virtue Amine is many drugs, natural products and the basic structural unit with bioactive compound, agriculture chemicals fungicide, drug, There is very important effect in the synthesis of high molecular material etc., is applied to the conjunction of industrial production and medicine intermediate At and preparation.

Traditional copper catalysis Ullmann reaction needs harsh reaction condition such as: the copper reagent of stoichiometry, high reaction Temperature (210 DEG C) and reaction time are longer, and yield is relatively low.With the rapid anti-exhibition of organotransition metal chemistry, people The catalyst that is reacted using other metals such as Ni, Pd as Ullmann, with the continuous deepening of research, Pd, Ni catalysis reaction Latent defect be also gradually exposed, specifically include that (1) is more toxic, since palladium belongs to heavy metal, have biggish poison Property, therefore limit extensive use of the palladium-catalyzed reaction in pharmaceuticals industry；(2) it is higher to belong to rare metal, price for palladium, needs It is recycled in the industrial production；(3) there is dependence to unstable, expensive and hypertoxic organophosphorus ligand, is urged in palladium and nickel In the reaction of change, the ligand used is almost to have more supervirulent organic phosphine compound entirely, except individual more steady in air Fixed outer, remaining is all more sensitive to air, thus preparation, using these ligands when just seem extremely inconvenient and uneasy Entirely.Therefore, copper catalysis is still top-priority selection.

The copper catalyst that Ullmann reaction uses is copper (I) and (II) valence salt, and wherein Cu (I) reagent is acknowledged as having There is real catalytic activity, Cu (I) reagent is with Cu₂Based on O, about Cu₂There are many research of O, but published Cu₂O micro mist is urged Change effect is undesirable, and especially reaction yield is low.

Summary of the invention

The first object of the present invention is to provide a kind of Cu₂O receives the preparation method of microcrystal, and diameter can be made in this method In 1.0 μm of Cu below₂O polyhedron, and pattern yield can be prepared greater than 95% with indices of diffraction crystal face { 311 } Cu₂Five decahedron of O.

The second object of the present invention is to provide a kind of Cu₂O receives microcrystal, and the crystalline size is small and uniform, and 50 The accounting of face body is high, for being catalyzed Ullmann reaction, has many advantages, such as that dosage is small, catalytic rate is high, yield is high.

In order to achieve the goal above, the present invention provides following technical schemes:

A kind of Cu₂O receives the preparation method of microcrystal, including the following steps:

The solution of the soluble-salt of copper is heated to 55~70 DEG C, aqueous slkali is added, precipitating is generated, reducing agent is then added Reduction reaction is carried out, is centrifuged later, is dry, obtaining Cu₂O receives microcrystal；

Wherein, the aqueous slkali is at least one of NaOH aqueous solution and KOH aqueous solution；

Solvent used in the solution of the soluble-salt of the copper is at least one of water and ethyl alcohol, is preferably at least contained Water；

The reducing agent is the mixture of ascorbic acid and hydroxylamine hydrochloride.

Usually with the Cu of the high indices of crystallographic plane₂O micro particles and nanoparticle chemical activity with higher, such as with The Cu of indices of diffraction crystal face { 311 }₂Five decahedron of O is proved to catalytic activity with higher, for this purpose, the present invention is in Traditional liquid phase Reducing agent type is improved on the basis of reduction method, improves above-mentioned Cu₂The decahedral pattern yield of O five and reduction size.Tool Body, the present invention is mixed to restore reactive material using two kinds of reducing agents, and reducing power is gone back than glucose Proper energy power is strong, and obtained Cu₂It is smaller that O receives micron polyhedron average grain diameter, while also effectively improving nucleation rate and increasing Add the quantity of core.

It is verified, when reducing agent is using the mixture of ascorbic acid and hydroxylamine hydrochloride, obtain Cu₂O, which receives in microcrystal, to be had There is the Cu of indices of diffraction crystal face { 311 }₂The decahedral pattern yield of O five is 95% or more, and partial size is at 1.0 μm or less.

The reaction temperature of mantoquita and aqueous slkali is unsuitable excessively high in the present invention, and the aggregation that will form blur margin when excessively high produces Object, polyhedron yield are extremely low；Reaction temperature is also unsuitable too low, too low to will form shaggy polyhedron, can be 55~70 It is optional within the scope of DEG C, such as 55 DEG C, 57 DEG C, 60 DEG C, 65 DEG C, 67 DEG C or 70 DEG C etc., such as 60~65 DEG C of preferred range.In addition, For the uniformity for improving crystalline size and pattern, it is preferred to use the mode of constant temperature keeps permanent for example, by using the means of heating water bath Temperature.

The solvent of the solution of the soluble-salt of copper can be pure water or ethyl alcohol or water and ethyl alcohol with any than mixing.

There are many drying means of the present invention after centrifugation, is including but not limited to dried in vacuo.

The present invention optimizes other reaction conditions on the basis of above, to improve five decahedron yields, reduce cost or drop Humble nanometer particle size, it is specific as follows.

The soluble-salt of copper of the present invention refers to the salt in water or ethyl alcohol with good solubility, including but not limited to One or more of nitrate, chlorate, acetate.Salt of the present invention can be containing the crystallization water or without the crystallization water Salt.

Preferably, solvent used in the solution of the soluble-salt of the copper are as follows: water and ethyl alcohol are with 14:1-10:1 volume ratio group At such as 14:1,13.5:1,13:1,12:1,12.5:1,11:1,11.5:1,10.5:1,10:1 etc..

Preferably, the concentration of the solution of the soluble-salt of the copper be 1.0~1.2 μm of ol/mL, such as 1.0 μm of ol/mL, 1.1 μm of ol/mL, 1.2 μm of ol/mL etc..

Preferably, the concentration of the aqueous slkali is 5.0~12.0mol/L, such as 5.0mol/L, 6.0mol/L, 7.0mol/ L, 8.0mol/L, 9.0mol/L, 10.0mol/L, 11.0mol/L, 12.0mol/L etc., preferred range have: 8.0~ 10.0mol/L。

Preferably, after generation precipitating and the additions reducing agent continues 3~5min of stirring before, such as 3min, 3.5min, 4min, 4.5min, 5min etc..

Preferably, the reducing agent is added as an aqueous solution.

Preferably, the concentration of aqueous ascorbic acid is 0.02-0.5mol/L.

In some embodiments, the concentration of aqueous ascorbic acid be 0.02-0.1mol/L, such as 0.02mol/L, 0.03mol/L、0.04mol/L、0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、0.09mol/L、0.1mol/ L。

In some embodiments, the concentration of aqueous ascorbic acid be 0.1-0.3mol/L, such as 0.13mol/L, 0.15mol/L、0.18mol/L、0.2mol/L、0.23mol/L、0.25mol/L、0.28mol/L、0.3mol/L。

In some embodiments, the concentration of aqueous ascorbic acid be 0.3-0.5mol/L, such as 0.33mol/L, 0.35mol/L、0.38mol/L、0.4mol/L、0.243mol/L、0.45mol/L、0.48mol/L、0.5mol/L。

Preferably, the concentration of hydroxylamine hydrochloride aqueous solution is 0.02-0.5mol/L.

In some embodiments, the concentration of hydroxylamine hydrochloride aqueous solution be 0.02-0.1mol/L, such as 0.02mol/L, 0.03mol/L、0.04mol/L、0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、0.09mol/L、0.1mol/ L。

In some embodiments, the concentration of hydroxylamine hydrochloride aqueous solution be 0.1-0.3mol/L, such as 0.13mol/L, 0.15mol/L、0.18mol/L、0.2mol/L、0.23mol/L、0.25mol/L、0.28mol/L、0.3mol/L。

In some embodiments, the concentration of hydroxylamine hydrochloride aqueous solution be 0.3-0.5mol/L, such as 0.33mol/L, 0.35mol/L、0.38mol/L、0.4mol/L、0.243mol/L、0.45mol/L、0.48mol/L、0.5mol/L。

Preferably, the total concentration of the reducing agent aqueous solution is preferably 0.1-0.2mol/L, such as 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.17mol/L, 0.2mol/L etc..

In some embodiments, ascorbic acid and hydroxylamine hydrochloride are added to the water dissolution respectively in the present invention and obtain concentration The hydroxylamine hydrochloride solution that ascorbic acid solution and concentration for 0.1-0.2mol/L are 0.1-0.2mol/L.

Preferably, the volume ratio of the aqueous ascorbic acid and hydroxylamine hydrochloride aqueous solution be 1~5:1~5, such as 1:1, 2:1,3:1,4:1,5:1,1:2,1:3,1:4,1:5,2:3,5:4,3:2 etc..

Preferably, the time of the reduction reaction be 10~60min, such as 10min, 20min, 30min, 40min, 50min, 60min etc..

Cu made from the above method of the present invention₂O receives microcrystal with spies such as small and uniform, the five decahedron yield height of size Point is included at least with five decahedrons of flowering structure: being formed by square, trapezoidal and two kinds of hexagons by total side connection type Five decahedrons, wherein each square and four trapezoidal connections, it is each trapezoidal to connect with three hexagons with a square It connects.

Cu made from the above method of the present invention₂O receive microcrystal can be used for making semiconductor devices or catalysis Ullmann it is anti- It answers.When for being catalyzed Ullmann reaction, it is mainly used for heterocatalysis Ullmann reaction, including but not limited to catalysis Ullmann C-N the or C-O cross-coupling reaction or C-C coupling reaction of type.

It has also been found that Cu made from the above method of the present invention₂When O receives microcrystal for being catalyzed Ullmann reaction, Cu₂O is able to maintain good stability, and rear appearance keeps good before the reaction, and any collapsing and deformation do not occur, can reach excellent yet In the catalytic effect of existing product, the advantages that showing small catalyst amount, mild condition, high catalytic efficiency.

Cu of the invention₂O receive microcrystal as Ullmann reaction catalyst when, this field can be used in reaction condition Normal condition, or use for reference following reaction process:

There-necked flask is chosen, three mouthfuls are respectively connected to intake valve, condenser pipe and extraction valve, access protection on the top of condenser pipe Ball keeps whole device closed, device is placed in oil bath pan, then closes extraction valve, and opening intake valve is passed through argon gas and waits protecting It keeps full of intake valve is closed, extraction valve is opened, is closed after whole device is vacuumized, carry out repeatedly three times, to protect Card empties air.Intake valve is finally opened in the device full of argon gas, then ready in advance from the addition of extraction valve end The argon gas of Continuous aeration for a period of time again after drug (catalyst and reactant, solvent etc.), it is ensured that entire reaction is in no air Under the conditions of carry out, then closed whole device is reacted.

Cu of the invention₂When O receives microcrystal for semiconductor material or catalyst, it can be used alone, can also load It uses on specific carrier, or is used by other assemblings.

To sum up, compared with prior art, invention achieves following technical effects:

(1)Cu₂O receives the smaller of microcrystal, and partial size is at 1.0 μm or less；

(2)Cu₂The five decahedral pattern yields that O receives in microcrystal with indices of diffraction crystal face { 311 } are high, 95% with On；

(3)Cu₂O receive microcrystal preparation method it is simple, quickly；

(4)Cu₂When O receives microcrystal for being catalyzed Ullmann reaction, with stability is good, catalyst amount is small, condition temperature The advantages that with high catalytic efficiency.

Detailed description of the invention

By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.

Fig. 1 is Cu prepared by the embodiment of the present invention 1 to 4₂O receives the shape appearance figure of microcrystal；

Fig. 2 is the Cu that embodiment 3 obtains₂Five decahedral X-ray diffraction in O polyhedron, corresponding { 110 } crystal face, { 111 } crystal face, { 201 } crystal face, { 221 } crystal face, { 311 } crystal face, { 222 } crystal face；

Fig. 3 is the Cu that embodiment 3 obtains₂Five decahedral FESEM in O polyhedron；

Fig. 4 and Fig. 5 be coupling reaction after different size size Cu2O receive microcrystalline solid phase powder FESEM figure.

Specific embodiment

Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.