阅读说明：本技术 一种基于Cu-BTC合成的碳壳包覆合金催化剂及其制备方法 (A kind of carbon shell clad alloy catalyst and preparation method thereof based on Cu-BTC synthesis ) 是由 马飞 单华强 陈冠君 于 2019-07-19 设计创作，主要内容包括：本发明公开了一种基于Cu-BTC合成的碳壳包覆合金催化剂及其制备方法,属于催化剂材料制备领域。首先合成Cu-BTC材料,对其高温煅烧形成Cu/C复合粉末,然后,将Cu/C复合粉末置于控温烘箱缓慢升温将其氧化成Cu<Sub>2</Sub>O/C复合粉末,最后,通过高温水热法,使不同金属负载在Cu<Sub>2</Sub>O表面,再通过酸处理将Cu<Sub>2</Sub>O除去以形成内部空心的壳层结构,同时Cu<Sub>2</Sub>O中部分Cu离子在酸处理过程中与其他金属结合形成合金,整个制备过程不会破坏Cu-BTC外面的碳膜,最终得到的材料为一种碳包覆的空壳的合金催化剂。本发明可以实现不同组分合金催化剂的合成,合金的空壳结构能够大幅度提高金属原子的暴露；由于金属合金被碳膜包裹,还能够有效阻止其在使用过程中的流失,从而显著提高合金催化剂的活性和稳定性。(The invention discloses a kind of carbon shell clad alloy catalyst and preparation method thereof based on Cu-BTC synthesis, belong to catalyst material preparation field.Cu-BTC material is synthesized first, Cu/C composite powder is formed to its high-temperature calcination, then, Cu/C composite powder is placed in temperature control oven slowly heats up and be oxidized to Cu 2 O/C composite powder, finally, making different metal be supported on Cu by high temperature hydro-thermal method 2 The surface O, then lead to peracid treatment for Cu 2 O is removed to form the shell structurre of boring, while Cu 2 Cu ion in part forms alloy in sour treatment process with other metal bondings in O, and whole preparation process will not destroy the carbon film outside Cu-BTC, and finally obtained material is a kind of alloy catalyst of carbon-coated ghost.The synthesis of different component alloy catalyst may be implemented in the present invention, and the hollow shell structure of alloy can increase substantially the exposure of metallic atom；Since metal alloy is wrapped up by carbon film, additionally it is possible to its loss in use is effectively prevented, to significantly improve the activity and stability of alloy catalyst.)

1. a kind of carbon shell clad alloy catalyst based on Cu-BTC synthesis, which is characterized in that the carbon shell clad alloy catalysis The structure of agent is to be coated with metal M and Cu in carbon ghost；The metal M is other metals in addition to Cu；The carbon shell is more Face body structure.

2. a kind of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 1, which is characterized in that institute Stating metal M is unitary metal or multicomponent alloy.

3. a kind of preparation method of the carbon shell clad alloy catalyst based on Cu-BTC synthesis, which is characterized in that including following step It is rapid:

(1) Cu/C composite powder will be generated after powdery Cu-BTC calcining, Cu will be generated after the oxidation of Cu/C composite powder₂O/C composite powder End；

(2) by Cu₂O/C composite powder is soluble in water, forms Cu₂O/C aqueous solution, in Cu₂Metal salt is added in O/C aqueous solution, so The pH value of Sodium Polyacrylate adjusting solution is added afterwards to 8-9, forms reaction system；Reaction is obtained after reaction system hydro-thermal reaction to produce The pH value of reaction product solution is adjusted to 1.5-3 by nitric acid by object solution, and the reaction product solution after being acidified will be sour Reaction product solution centrifugal treating after change will obtain carbon shell clad alloy catalyst after centrifugation product washing and drying.

4. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 3, It is characterized in that, in step (1), the calcination temperature of powdery Cu-BTC is 500-700 DEG C, calcination time 1-3h.

5. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 3, It is characterized in that, in step (1), Cu/C composite powder oxidizing temperature is 70-90 DEG C, oxidization time 7-9h.

6. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 3, It is characterized in that, in step (2), Cu₂In O/C aqueous solution, Cu₂The concentration of O/C is (0.1-0.6) mg/mL.

7. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 3, It is characterized in that, in step (2), hydrothermal temperature is 110-130 DEG C, the hydro-thermal reaction time 5-8h.

8. special according to a kind of preparation method for carbon shell clad alloy catalyst based on Cu-BTC synthesis that claim 3 is stated Sign is, in step (1), the preparation process of powdery Cu-BTC is that nitrate trihydrate copper is dissolved in methanol, forms solution A；It will gather Vinylpyrrolidone and 1.3.5- benzenetricarboxylic acid are dissolved in methanol, form solution B；Solution A and solution B be respectively after ultrasonic disperse, Solution A and solution B are mixed and continue to stir, forming process Cu-BTC will obtain centrifugation and produce after process Cu-BTC centrifugal treating Object will form powdery Cu-BTC after centrifugation product washing drying.

9. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 8, It is characterized in that, in solution A, the mixed proportion of nitrate trihydrate copper and methanol is (2-10) g:(50-200) mL；In solution B, poly- second The mixed proportion of alkene pyrrolidone and methanol is (0.5-2) g:(50-200) mL, the mixing ratio of 1.3.5- benzenetricarboxylic acid and methanol Example is (1.5-5) g:(50-200) mL.

10. a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis according to claim 8, It is characterized in that, the mixed volume ratio of solution A and solution B is 1:1.

[technical field]

The invention belongs to catalyst material preparation fields, and in particular to a kind of carbon shell clad alloy based on Cu-BTC synthesis Catalyst and preparation method thereof.

[background technique]

Fossil energy consumes the principal element for having become and hindering progress of human society and development in science and technology excessively, and causes One of main source of environmental pollution.Since the 21th century, countries in the world all are making great efforts to develop new clean energy technology, Such as: solar energy, catalysis aquatic products hydrogen oxygen, fuel cell power generation, wherein the exploitation and use of catalyst material are to guarantee these Energy technology is capable of one of the critical material of commercialization.

Theoretically, catalyst is to refer to change reactant chemical reaction rate and the quality of itself and chemical property not The substance that can be changed, and in fact, catalyst is in actual use often because of the complicated feelings in chemical reaction Condition and dissolution occurs, is lost, poisoning even complete deactivation.Therefore, design high-performance and stable catalyst how to be developed just Become particularly important.

In recent years, alloying and structure design are considered as effectively solving the problems, such as primary hand present in above-mentioned catalyst Section.Reason is not only to will affect its electronic structure after different metal alloying, moreover it is possible to be obviously improved steady in catalytic process It is qualitative, change catalytic performance.If taking the structure and morphology of other means control metal alloy again while alloying, make it More surfaces are exposed, then can further improve the activity of catalyst.

[summary of the invention]

It is an object of the invention to overcome the above-mentioned prior art, a kind of carbon shell packet based on Cu-BTC synthesis is provided Laminating Au catalyst and preparation method thereof；The preparation method prepares a kind of hollow shell structure of alloy, on the one hand can be significantly The exposure for improving metallic atom, in addition, metal alloy is wrapped up by carbon film, additionally it is possible to the loss in its catalytic process is effectively prevented, To significantly improve its catalytic activity and stability, practical value with higher.

In order to achieve the above objectives, the present invention is achieved by the following scheme:

A kind of carbon shell clad alloy catalyst based on Cu-BTC synthesis, the structure of the carbon shell clad alloy catalyst are Metal M and Cu are coated in carbon ghost；The metal M is other metals in addition to Cu；The carbon shell is polyhedral structure.

Preferably, the metal M is unitary metal or multicomponent alloy.

A kind of preparation method of the carbon shell clad alloy catalyst based on Cu-BTC synthesis, comprising the following steps:

(1) Cu/C composite powder will be generated after powdery Cu-BTC calcining, Cu will be generated after the oxidation of Cu/C composite powder₂O/C Composite powder；

(2) by Cu₂O/C composite powder is soluble in water, forms Cu₂O/C aqueous solution, in Cu₂Metal is added in O/C aqueous solution Then salt is added the pH value of Sodium Polyacrylate adjusting solution to 8-9, forms reaction system；It is obtained after reaction system hydro-thermal reaction The pH value of reaction product solution is adjusted to 1.5-3 by nitric acid by reaction product solution, and the reaction product after being acidified is molten Reaction product solution centrifugal treating after acidification will be obtained carbon shell clad alloy catalyst after centrifugation product washing and drying by liquid.

A further improvement of the present invention is that:

Preferably, in step (1), the calcination temperature of powdery Cu-BTC is 500-700 DEG C, calcination time 1-3h.

Preferably, in step (1), Cu/C composite powder oxidizing temperature is 70-90 DEG C, oxidization time 7-9h.

Preferably, in step (2), Cu₂In O/C aqueous solution, Cu₂The concentration of O/C is (0.1-0.6) mg/mL.

Preferably, in step (2), hydrothermal temperature is 110-130 DEG C, the hydro-thermal reaction time 5-8h.

Preferably, in step (1), the preparation process of powdery Cu-BTC is that nitrate trihydrate copper is dissolved in methanol, is formed molten Liquid A；Polyvinylpyrrolidone and 1.3.5- benzenetricarboxylic acid are dissolved in methanol, solution B is formed；Solution A and solution B are respectively ultrasonic After dispersion, solution A and solution B are mixed and continue to stir, forming process Cu-BTC will be obtained after process Cu-BTC centrifugal treating It is centrifuged product, powdery Cu-BTC will be formed after centrifugation product washing drying.

Preferably, in solution A, the mixed proportion of nitrate trihydrate copper and methanol is (2-10) g:(50-200) mL；Solution B In, the mixed proportion of polyvinylpyrrolidone and methanol is (0.5-2) g:(50-200) mL, 1.3.5- benzenetricarboxylic acid and methanol Mixed proportion is (1.5-5) g:(50-200) mL.

Preferably, the mixed volume ratio of solution A and solution B is 1:1.

Compared with prior art, the invention has the following advantages:

The invention discloses a kind of carbon shell clad alloy catalyst based on Cu-BTC synthesis, alloy is coated in the carbon shell Catalyst, carbon shell as skeleton structure in the periphery of entire catalyst, inside be enclosed with alloy, internal alloy is Cu and M The alloy of formation, the structure enable the catalyst to be adjusted according to different application fields because M can be any alloy Its whole types of alloys, the hollow shell structure including this alloy are greatly improved the exposure of metallic atom, improve urging for catalyst Change effect；Because alloy is wrapped in inside carbon shell, the stable structure of carbon shell, so that the catalyst can have in catalytic process Effect stops alloy to be corroded and be lost in catalytic process, to significantly improve its catalytic activity and stability.

Further, metal M can unitary metal or multicomponent alloy, type and quantity can according to catalyst be applicable in Field and requirement are adjusted, so that the carbon shell clad alloy catalyst is applied widely.

The invention also discloses a kind of preparation method of carbon shell clad alloy catalyst based on Cu-BTC synthesis, the preparations Cu-BTC calcining is become Cu/C composite powder first by method, then Cu/C composite powder is oxidized into Cu₂O/C composite powder； By in Cu₂Metal salt is added in O/C aqueous solution and forms reaction system, reaction system is obtained after hydro-thermal reaction inside carbon shell It is coated with alloy catalyst.In above-mentioned preparation process, the connecting key of the Cu-BTC of powdery internal Cu and C in calcination process is disconnected It splits, so that the compound middle Cu of obtained Cu/C is coated by C, then C shell is formed by oxidation process and coats Cu₂The structure of O；It is logical It crosses and metal salt is added to Cu₂In O aqueous solution, the pH of entire reaction system is first adjusted to alkalinity, entire reaction system is in also Former environment, the metal ion of addition is by Cu₂Cu in O is restored, then by acidification, removes Cu existing for carbon shell inside₂O, Ultimately form the alloy catalyst structure of carbon shell cladding；Whole preparation process will not destroy the skeleton carbon film outside Cu-BTC, and Alloy is wrapped in inside carbon shell by stable, and preparation process is novel, is had broad application prospects.

[Detailed description of the invention]

Fig. 1 is the XRD spectrum of product shown in embodiment 1；

Fig. 2 is SEM the and EDS map of product morphology shown in embodiment 1；

Wherein, (a) figure is SEM figure；(b) figure is EDS figure；

Fig. 3 is the TEM map of product shown in embodiment 1；

Fig. 4 is the XRD spectrum of product shown in embodiment 2；

Fig. 5 is SEM the and EDS map of product morphology shown in embodiment 2；

Wherein, (a) figure is SEM figure；(b) figure is EDS figure；

Fig. 6 is the TEM map of product shown in embodiment 2.

[specific embodiment]

The invention will be described in further detail in the following with reference to the drawings and specific embodiments, and the invention discloses one kind to be based on The carbon shell clad alloy catalyst and preparation method thereof of Cu-BTC synthesis, the preparation method specifically includes the following steps:

Step 1, the methanol of two parts of same volumes is weighed, first by nitrate trihydrate copper (Cu (NO₃)₂·3H₂O) it is dissolved in a copy of it Methanol is simultaneously vigorously stirred, and nitrate trihydrate copper is quickly dissolved in methyl alcohol, obtains solution A, wherein nitrate trihydrate copper Mixed proportion with methanol is (2-10) g:(50-200) mL；Appropriate polyvinylpyrrolidone and 1.3.5- benzenetricarboxylic acid are dissolved in Another methanol, obtains solution B, wherein the mixed proportion of the polyvinylpyrrolidone and methanol that are added is (0.5-2) g:(50- 200) mL, the 1.3.5- benzenetricarboxylic acid of addition and the mixed proportion of methanol are (1.5-5) g:(50-200) mL；Solution A and solution B After being respectively ultrasonically treated 10min with power 150W, the solution A after ultrasound is poured into separatory funnel, with speed 100-400 μ L/min In solution B after instilling ultrasound and continue to stir, the mixed volume ratio of solution A and solution B is 1:1；After the completion of instillation, persistently stir Mix after 20-40h can forming process Cu-BTC, centrifugal treating process Cu-BTC, centrifugal speed 7000r/min, centrifugation time For 8min, centrifugation product is obtained, washs centrifugation product 6 times, ethyl alcohol/deionized water mixed liquor with ethyl alcohol/deionized water mixed liquor In ethyl alcohol and the volume ratio of deionized water be 1:1, with the increase of washing times, the ratio of ethyl alcohol at the uniform velocity in increase mixed liquor Product after washing is placed in the drying of vacuum drying oven room temperature, will dried by example until solution used is pure ethyl alcohol when the 6th washing Dry product is pulverized, and obtains the Cu-BTC of powdery, for use；20-40h is persistently stirred in reaction process in the step, so that C The enough reaction time is provided with Cu bonding, to form Cu-BTC.

Step 2, the powdery Cu-BTC prepared is put into vacuum tube furnace, calcines 1-3h under an inert atmosphere, calcined Temperature is 500-700 DEG C, and heating rate is 2 DEG C/min, and Cu/C composite powder is obtained after calcining, and the inert atmosphere is 99.9% Argon gas；It is put into slow heating and oxidation in temperature control oven after the Cu/C composite powder that calcining obtains is ground, is in temperature control oven Air atmosphere, heating rate are 15 DEG C/h, and holding temperature is 70-90 DEG C, and soaking time 7-9h forms it into Cu₂O/C is compound Powder；In the step process, the connecting key fracture of the Cu-BTC of powdery internal Cu and C in calcination process, so that obtained Cu/ The compound middle Cu of C is coated by C, because the structure of C itself has the C outside Cu itself compared with multiple hole, subsequent In temperature control oven during heating and oxidation, Cu is oxidized, and ultimately forms Cu₂O/C composite powder.

Step 3, by Cu₂O/C composite powder is soluble in water, Cu₂The mass concentration of O/C in water is (0.1-0.6) mg/mL, Form Cu₂O/C aqueous solution, persistently stirs Cu₂Other metal (M) salt substances are added simultaneously and form mixed liquor for O/C aqueous solution, are added The amount of metal salt has no particular requirement, and the amount of metal that can be loaded according to actual needs is added, the metal salt of addition such as: chlorination Palladium, ruthenic chloride, potassium chloroplatinite, cobalt chloride, nickel chloride etc., and the subject alloy that can prepare as needed while a variety of gold are added Belong to salt；Then, mixed liquor pH value is adjusted to 8-9 with the sodium polyacrylate solution that mass concentration is 50%, continue to stir 5- 30min forms reaction system, and reaction system is poured into sealing in reaction kettle and carries out hydro-thermal reaction, hydrothermal temperature 110- 130 DEG C, the hydro-thermal reaction time 5-8h, the solution that reaction obtains is placed on magnetic stirring apparatus after the reaction was completed, stirring condition Solution ph is adjusted to 1.5-3 by lower instillation nitric acid, and the reaction product solution after being acidified is again through centrifugation, washing, drying, i.e., Obtain carbon coating ghost alloy catalyst ([email protected])；In the reaction process, by metal salt and Cu₂In O/C composite powder aqueous solution After mixing, pH value is adjusted to by alkalinity by Sodium Polyacrylate, so that entire reaction system is in molten alkaline reduction atmosphere, by metal Metal ions M in salt restores, while Sodium Polyacrylate can be as the surfactant in hydrothermal reaction process, so that most End form at composite construction [email protected] stablize；Hydrothermal reaction process, the metal ions M being reduced out pass through the hole of C film, metal Ion M is supported on Cu₂The surface O, then lead to peracid treatment for Cu₂O is removed, and forms the shell structurre of boring, while part Cu₂O In Cu ion in sour treatment process with M formed alloy, since whole preparation process will not destroy the carbon film outside Cu-BTC, Therefore finally obtained material is a kind of CuM alloy catalyst of carbon ghost cladding；M herein can be various metals, such as work as M For Pt and Pd, then finally formed structure is carbon coating ghost PtPdCu alloy, is ternary alloy three-partalloy inside C ghost；Of the invention Technical thought is clearly novel, and prepared product can increase substantially the utilization rate of noble metal, has broad application prospects.

The invention discloses it is a kind of based on Cu-BTC synthesis carbon coating ghost PtPdCu alloy catalyst preparation method, Firstly, then synthesis Cu-BTC material carries out high-temperature calcination to it under an inert atmosphere and forms Cu/C composite powder, it then, will Cu/C, which is placed in temperature control oven and slowly heats up, is oxidized to Cu₂O/C, finally, making M be supported on Cu by high temperature hydrothermal method₂O Surface, then lead to peracid treatment for Cu₂O is removed, and forms the shell structurre of boring, while part Cu₂Cu ion in O is in acid Subject alloy is formed in treatment process in conjunction with M, since whole preparation process will not destroy the carbon film outside Cu-BTC, Finally obtained material is a kind of MCu alloy catalyst of carbon-coated ghost.

By first synthesizing Cu-BTC material, using calcining, oxidation and high temperature hydro-thermal and etc., prepare a kind of carbon packet Ghost alloy catalyst is covered, by the way that different metallic salts is added, realizes the synthesis of different component alloy catalyst, the sky of alloy Shell structure can increase substantially the exposure of metallic atom, in addition, metal alloy is wrapped up by carbon film, additionally it is possible to effectively it be prevented to urge Loss during change, so that its catalytic activity and stability are significantly improved, practical value with higher.