阅读说明：本技术 一种负载碳化钒的CoP微球三功能催化材料的制备方法及其应用 (Preparation method and application of CoP microsphere three-functional catalytic material loaded with vanadium carbide ) 是由 次素琴 吴罗生 张腾 赵志锋 于 2020-04-28 设计创作，主要内容包括：本发明公布了一种负载碳化钒的CoP微球三功能催化材料的制备及其应用,即一种能催化尿素降解,析氢反应(HER)和析氧反应(OER)的三功能催化剂。将均苯三甲酸(C<Sub>9</Sub>H<Sub>6</Sub>O<Sub>6</Sub>)、对苯二甲酸(C<Sub>8</Sub>H<Sub>6</Sub>O<Sub>4</Sub>)、六水合硝酸钴(Co(NO<Sub>3</Sub>)<Sub>2</Sub>.6H<Sub>2</Sub>O)、P-123和偏钒酸铵(NH<Sub>4</Sub>VO<Sub>3</Sub>)溶于乙二醇和去离子水的混合溶剂,再往其中加入一定量的醋酸,搅拌均匀后进行水热反应,制得V/Co-MOF前躯体,再将前驱体进行低温空烧,得到V<Sub>8</Sub>C<Sub>7</Sub>/Co<Sub>3</Sub>O<Sub>4</Sub>中间体,以次磷酸钠为磷源,将V<Sub>8</Sub>C<Sub>7</Sub>/Co<Sub>3</Sub>O<Sub>4</Sub>中间体和次磷酸钠按一定比例置于同一瓷舟的两端,将磷源放置在气流上游,在惰性气氛下置于管式炉中低温煅烧,得到V<Sub>8</Sub>C<Sub>7</Sub>/CoP催化材料。该催化剂制备方法简易且在电催化尿素降解和产氢方面均具有潜在应用价值。(The invention discloses preparation and application of a CoP microsphere three-function catalytic material loaded with vanadium carbide, namely a three-function catalyst capable of catalyzing urea degradation, Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Mixing trimesic acid (C) 9 H 6 O 6 ) Terephthalic acid (C) 8 H 6 O 4 ) Cobalt nitrate hexahydrate (Co (NO) 3 ) 2 .6H 2 O), P-123 and ammonium metavanadate (NH) 4 VO 3 ) Dissolving in mixed solvent of ethylene glycol and deionized water, adding a certain amount of acetic acid, uniformly stirring, carrying out hydrothermal reaction to obtain a V/Co-MOF precursor, and carrying out low-temperature air-firing on the precursor to obtain the final productTo V 8 C 7 /Co 3 O 4 Intermediate, sodium hypophosphite is used as phosphorus source, and V is 8 C 7 /Co 3 O 4 The intermediate and sodium hypophosphite are placed at two ends of the same porcelain boat according to a certain proportion, a phosphorus source is placed at the upstream of the air flow, and the porcelain boat is placed in a tubular furnace under inert atmosphere for low-temperature calcination to obtain V 8 C 7 a/CoP catalytic material. The catalyst is simple in preparation method and has potential application value in the aspects of electro-catalysis urea degradation and hydrogen production.)

1. A preparation method of a CoP microsphere three-functional catalytic material loaded with vanadium carbide is characterized by comprising the following steps:

1) preparation of V/Co-MOF-0.18 precursor material

0.9894g of Co (NO)₃)₂·6H₂O, 0.0702g NH₄VO₃0.5g of P-123, 0.105g of C₉H₆O₆And 0.125g of C₈H₆O₄Dissolving in 60m L mixed solvent of ethylene glycol and deionized water, stirring to mix well, adding 2.4m L acetic acid to adjustAnd (3) pouring the solution into a liner of a 100m L reaction kettle, heating to 180 ℃, reacting for 24 hours, washing with absolute ethyl alcohol and deionized water, filtering, and finally drying in vacuum to obtain a V/Co-MOF precursor.

2)V₈C₇/Co₃O₄Preparation of-0.18 intermediate Material

And putting the precursor powder solid obtained in the step (A) into a muffle furnace, heating to 450 ℃, and calcining for 2 h. To obtain V₈C₇/Co₃O₄An intermediate.

3)V₈C₇Preparation of/CoP-0.18 catalytic Material

Sodium hypophosphite is used as a phosphorus source, and V is added₈C₇/Co₃O₄Placing the-0.18 intermediate and sodium hypophosphite at the mass ratio of 1:20 at two ends of the same porcelain boat, placing a phosphorus source at the upstream of an airflow, heating to 350 ℃ in a tube furnace under the argon atmosphere, calcining for 2h, cooling to room temperature, and taking out a product to obtain V₈C₇A/CoP-0.18 microspherical catalyst.

2. The preparation method of the CoP microsphere three-functional catalytic material loaded with vanadium carbide according to claim 1, which is characterized in that: the volume ratio of the ethylene glycol to the deionized water in the adopted mixed solvent is 2: 1.

3. the preparation method of the CoP microsphere three-functional catalytic material loaded with vanadium carbide according to claim 1, which is characterized in that: co (NO)₃)₂·6H₂O and NH₄VO₃The molar ratio of the two is 3.4: 0.6.

4. the preparation method of the CoP microsphere three-functional catalytic material loaded with vanadium carbide according to claim 1, which is characterized in that: the temperature of the hydrothermal reaction is 180 ℃, and the reaction time is 24 h.

5. The preparation method of the CoP microsphere three-functional catalytic material loaded with vanadium carbide according to claim 1, which is characterized in that: the air-firing temperature is 450 ℃, and the air-firing time is 2 hours.

6. The preparation method of the CoP microsphere three-functional catalytic material loaded with vanadium carbide according to claim 1, which is characterized in that: v₈C₇/Co₃O₄The mass ratio of the intermediate to the sodium hypophosphite at low temperature of 0.18 is 1: 20.

Technical Field

The invention relates to the technical field of catalyst preparation methods, in particular to a preparation method and application of a CoP microsphere three-functional catalytic material loaded with vanadium carbide.

Background

At present, with the exhaustion of fossil fuels and the aggravation of global environmental crisis, the utilization of clean and efficient sustainable energy sources to replace fossil fuels is urgent. Because hydrogen energy has the advantages of high energy conversion efficiency, abundant sources, clean products and the like, the hydrogen energy is very likely to become a substitute of fossil fuels. Among the numerous hydrogen production methods, electrochemical hydrogen production is considered as a promising approach, and the high overpotential of the cathode and anode has hindered the development of electrochemical hydrogen production. Albeit platinum carbon and RuO₂HER and OER catalysts considered to perform best, but platinum carbon and RuO₂The industrial application of noble metal-based catalysts is limited by the scarcity of noble metals and the poor stability of platinum catalysts, so that the research on high-activity non-noble metal or non-metal catalysts with low price needs to replace the noble metal-based catalysts.

In recent years, transition metal phosphide has outstanding catalytic activity of HER, OER and Urea Oxidation Reaction (UOR) and is widely researched, but the conductivity of the transition metal phosphide is poor, so that the performance of the transition metal phosphide catalytic material is further improved, and the problem to be solved by the industry is solved.

Disclosure of Invention

The invention aims to solve the problems that: providing a load V₈C₇The synthesis method of the CoP microspheres provides a three-functional catalyst which is simple to prepare and can be widely applied, and the catalyst has excellent catalytic hydrogen evolution reaction performance under alkaline and acidic conditions and can catalyze urea degradation to assist in hydrogen production. The load V₈C₇The synthesis method of the CoP microsphere catalyst comprises the following steps:

1) preparation of V/Co-MOF-0.18 precursor material

0.9894g of Co (NO)₃)₂·6H₂O, 0.0702g NH₄VO₃0.5g of P-123, 0.105g of C₉H₆O₆And 0.125g of C₈H₆O₄Dissolving the mixture in a mixed solvent of 60m L ethylene glycol and deionized water, stirring to fully and uniformly mix the mixture, adding 2.4m L acetic acid to regulate the pH value, pouring the solution into a liner of a 100m L reaction kettle, heating to 180 ℃ for reaction for 24 hours, washing with absolute ethyl alcohol and deionized water, filtering, and finally performing vacuum drying to obtain a V/Co-MOF precursor.

2)V₈C₇/Co₃O₄Preparation of-0.18 intermediate Material

And putting the precursor powder solid obtained in the step (A) into a muffle furnace, heating to 450 ℃, and calcining for 2 h. To obtain V₈C₇/Co₃O₄An intermediate.

3)V₈C₇Preparation of/CoP-0.18 catalytic Material

Sodium hypophosphite is used as a phosphorus source, and V is added₈C₇/Co₃O₄Placing the-0.18 intermediate and sodium hypophosphite at the mass ratio of 1:20 at two ends of the same porcelain boat, placing a phosphorus source at the upstream of an airflow, heating to 350 ℃ in a tube furnace under the argon atmosphere, calcining for 2h, cooling to room temperature, and taking out a product to obtain V₈C₇A/CoP-0.18 microspherical catalyst.

Preferably, the method (1) is characterized in that the volume ratio of the ethylene glycol to the deionized water in the mixed solvent is 2: 1.

preferably, it (1) is characterized by Co (NO)₃)₂·6H₂O and NH₄VO₃The molar ratio of the two is 3.4: 0.6.

preferably, the (1) is characterized in that the temperature of the hydrothermal reaction is 180 ℃ and the reaction time is 24 h.

Preferably, the (2) is characterized in that the empty burning temperature is 450 ℃ and the empty burning time is 2 h.

Preferably, it (3) is characterized by V₈C₇/Co₃O₄The mass ratio of the intermediate to the sodium hypophosphite at low temperature of 0.18 is 1: 20.

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

V₈C₇the CoP microspheres are loaded, so that the conductivity and the mass-to-charge conductivity of the whole material are improved. And the catalyst has excellent catalytic hydrogen evolution reaction performance under alkaline and acidic conditions and can catalyze urea degradation to assist in hydrogen production.

Drawings

FIG. 1 is V₈C₇XRD pattern of/CoP-0.18 material;

FIG. 2 is V₈C₇a/CoP-0.18 material scanning electron microscope picture;

FIG. 3 is V₈C₇HER polarization curve of/CoP-0.18 material under alkalinity;

FIG. 4 is V₈C₇OER polarization curve of/CoP-0.18 material under alkalinity;

FIG. 5 is V₈C₇The stability test performance diagram of the/CoP-0.18 material in an acid-base asymmetric electrolytic cell.

Detailed Description

The present invention is further described by the following embodiments with reference to the drawings, but it should be noted that the embodiments are not to be construed as limiting the scope of the present invention.