阅读说明：本技术 木头基多孔活化碳/Ni0.2Mo0.8N电催化材料及其制备方法 (Wood-based porous activated carbon/Ni0.2Mo0.8N electro-catalytic material and preparation method thereof ) 是由 赵雷 袁雨禾 陈辉 方伟 何漩 杜星 李薇馨 王大珩 于 2021-08-31 设计创作，主要内容包括：本发明涉及一种木头基多孔活化碳/Ni-(0.2)Mo-(0.8)N电催化材料及其制备方法。其技术方案是：将预处理后的木块浸渍于15～30wt％的ZnCl-(2)溶液中,于105～115℃条件下处理45～50小时,再于高纯氩气气氛和800～900℃条件下热处理2～4小时,洗涤,得到木头基多孔活化碳材料；将Na-(2)MoO-(4)·2H-(2)O和NiCl-(2)·6H-(2)O加入到去离子水中,搅拌,搅拌后加入到水热反应釜中,然后加入所述木头基多孔活化碳材料,在150～170℃条件下热处理5～7小时,自然冷却,取出后洗涤和干燥,最后在氨气气氛和550～650℃条件下热处理10～30分钟,制得木头基多孔活化碳/Ni-(0.2)Mo-(0.8)N电催化材料。本发明工艺简单、成本低廉和环境友好,所制制品能在酸性和碱性条件下稳定电解水。(The invention relates to wood-based porous activated carbon/Ni 0.2 Mo 0.8 N electrocatalytic material and a preparation method thereof. The technical scheme is as follows: dipping the pretreated wood block in 15-30 wt% of ZnCl 2 Treating the solution at 105-115 ℃ for 45-50 hours, then treating the solution at 800-900 ℃ for 2-4 hours in a high-purity argon atmosphere, and washing to obtain a wood-based porous activated carbon material; mixing Na 2 MoO 4 ·2H 2 O and NiCl 2 ·6H 2 Adding O into deionized water, stirring, adding into a hydrothermal reaction kettle after stirring, then adding the wood-based porous activated carbon material, and carrying out reaction at the temperature of 150-170 DEG CPerforming heat treatment for 5-7 hours, naturally cooling, taking out, washing and drying, and finally performing heat treatment for 10-30 minutes in an ammonia atmosphere at 550-650 ℃ to obtain the wood-based porous activated carbon/Ni 0.2 Mo 0.8 An N electrocatalytic material. The invention has simple process, low cost and environmental protection, and the prepared product can stably electrolyze water under acidic and alkaline conditions.)

1. Wood-based porous activated carbon/Ni_0.2Mo_0.8The preparation method of the N electrocatalytic material is characterized by comprising the following steps:

cutting the wood into blocks, washing the blocks with deionized water for 2-3 times, and drying the blocks at the temperature of 55-65 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block into 3-5 parts by mass of the pretreated wood block15 to 30 wt% of ZnCl₂Treating the wood blocks in the solution at 105-115 ℃ for 45-50 hours to obtain wood blocks treated by zinc chloride; carrying out heat treatment on the wood block treated by the zinc chloride for 2-4 hours under the conditions of high-purity argon atmosphere and 800-900 ℃, washing with deionized water for 3-4 times, and drying to obtain a wood-based porous activated carbon material;

step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 1-2 parts by mass of NiCl₂·6H₂Adding O into 97-98 parts by mass of deionized water, and stirring for 10-20 minutes to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 3-5 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 150-170 ℃ for 5-7 hours, naturally cooling to room temperature, taking out, washing with deionized water for 2-3 times, and drying for 24-48 hours to obtain wood-based porous activated carbon/NiMoO₄A material;

step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is subjected to heat treatment for 10-30 minutes under the conditions of ammonia atmosphere and 550-650 ℃ to prepare the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

2. The wood-based porous activated carbon/Ni of claim 1_0.2Mo_0.8The preparation method of the N electro-catalysis material is characterized in that the wood is one of poplar wood, pine wood, basswood, bamboo, sapelli wood and maple wood.

3. The wood-based porous activated carbon/Ni of claim 1_0.2Mo_0.8The preparation method of the N electrocatalytic material is characterized in that the length, the width and the height of the wood block are (30-40) x (10-20) x (5-10) mm.

4. The wood-based porous activated carbon/Ni of claim 1_0.2Mo_0.8The preparation method of the N electrocatalytic material is characterized in that the purity of the high-purity argon is more than 99.999 percent.

5. The wood-based porous activated carbon/Ni of claim 1_0.2Mo_0.8The preparation method of the N electrocatalytic material is characterized in that the purity of the ammonia gas is more than 99.6 percent.

6. Wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material, characterized in that said wood-based porous activated carbon/Ni_0.2Mo_0.8The N electrocatalytic material is the wood-based porous activated carbon/Ni as claimed in any one of claims 1 to 5_0.2Mo_0.8Preparation method of N-electrocatalytic material for preparing wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

Technical Field

The invention belongs to the technical field of electrocatalytic materials. In particular to wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material and a preparation method thereof.

Background

The electrolysis of water to produce high purity hydrogen is considered an effective method to meet the growing energy demands. Electrolyzed water comprises two half-reactions: the hydrogen evolution reaction at the cathode and the oxygen evolution reaction at the anode. Therefore, the research and synthesis of the electrocatalyst with low cost, high performance and strong stability has great significance for industrial electrolyzed water. At present, although platinum-based materials and iridium oxide show good activity in hydrogen evolution and oxygen evolution reactions, respectively, the high cost and scarcity of noble metals hinder large-scale industrial application, so research and development of low-cost, high-activity and stable non-noble metal-based electrocatalysts for application in practical industrial electrolytic water become hot spots. Among many non-noble metal-based electrolytic water materials, transition metal nitrides, particularly NiMoN compounds, are widely concerned by researchers because the bonding energy of compounds formed by Ni and Mo and active hydrogen atoms is moderate and the compounds are favorable for hydrogen evolution reaction, and the nitrides have the characteristics of good conductivity and corrosion resistance.

For example, the patent technology of "a preparation method of vanadium doped transition metal nitride and application thereof" (CN110787824A) synthesizes V-NiMoN material on nickel foam by hydrothermal method, but nickel foam is easy to dissolve under acidic condition and is unstable during use.

Such as document I (Sangg H P, Jo T H, Min H L, et al. high ply active and stable nickel-molybdenum nitride (Ni)₂Mo₃N)electrocatalyst for hydrogen evolution[J]Journal of Materials Chemistry A,2021,9: 4945-4951) reports direct mixing of foamed nickel as a nickel source with molybdenum salt and urea, heat treatment under nitrogen atmosphere, and one-step synthesis of Ni₂Mo₃N electrocatalytic material, but the electrocatalytic hydrogen evolution reaction can be carried out only under alkaline conditions.

As reported in document II (Chang B, Yang J, Shao Y L, et al. metallurgical NiMoN nanowines with a reactive function: an ultra-effective biological activity for over water splitting [ J ]. ChemUSchem, 2018,11(18): 3198. cake 3207.), a DTAB surfactant was used in addition to a nickel salt and a molybdenum salt to synthesize NiMoN materials, and the synthesis steps were complicated and could not stabilize electrolyzed water under acidic conditions.

As reported in document III (Yin Z X, Sun Y, Zhu C L, et al, metallurgical Ni-Mo nitride nanoparticles as active and stable biochemical electrolytes for full water splitting [ J ]. Journal of Materials Chemistry A,2017,5: 13648-.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and aims to provide wood-based porous activated carbon/Ni which is simple in process, low in cost and environment-friendly_0.2Mo_0.8A preparation method of the N electrocatalytic material; the wood-based porous activated carbon/Ni prepared by the method_0.2Mo_0.8The N electrocatalytic material can stabilize electrolyzed water under acidic and alkaline conditions.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

step one, cutting the wood into blocks, washing with deionized water 2Drying for 3 times at 55-65 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block into 3-5 parts by mass of 15-30 wt% ZnCl₂Treating the wood blocks in the solution at 105-115 ℃ for 45-50 hours to obtain wood blocks treated by zinc chloride; and (3) carrying out heat treatment on the wood blocks treated by the zinc chloride for 2-4 hours under the conditions of high-purity argon atmosphere and 800-900 ℃, washing with deionized water for 3-4 times, and drying to obtain the wood-based porous activated carbon material.

Step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 1-2 parts by mass of NiCl₂·6H₂Adding O into 97-98 parts by mass of deionized water, and stirring for 10-20 minutes to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 3-5 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 150-170 ℃ for 5-7 hours, naturally cooling to room temperature, taking out, washing with deionized water for 2-3 times, and drying for 24-48 hours to obtain wood-based porous activated carbon/NiMoO₄A material.

Step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is subjected to heat treatment for 10-30 minutes under the conditions of ammonia atmosphere and 550-650 ℃ to prepare the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

The wood is one of poplar, pine, basswood, bamboo, sapelli wood and maple wood.

The length, width and height of the wood block are (30-40) x (10-20) x (5-10) mm.

The purity of the high-purity argon is more than 99.999%.

The purity of the ammonia gas is more than 99.6 percent.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:

1. the invention firstly soaks the pretreated wood block in ZnCl₂In the solution, performing heat treatment in a high-purity argon atmosphere at 800-900 ℃ to obtain a wood-based porous activated carbon material; then adding Na₂MoO₄·2H₂O、NiCl₂·6H₂O andadding the mixed solution of deionized water into a hydrothermal reaction kettle, adding a wood-based porous activated carbon material for hydrothermal reaction, and finally carrying out heat treatment in an ammonia atmosphere at 550-650 ℃ to obtain the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material. The invention does not need to use a surfactant, has simple process, saves the production cost and is environment-friendly.

2. The wood-based porous activated carbon/Ni synthesized by the invention_0.2Mo_0.8The N electrocatalysis material has strong corrosion resistance because the substrate material is a wood-based porous activated carbon material, and cannot be corroded by acid or alkali, so that the N electrocatalysis material can stabilize electrolyzed water under acidic and alkaline conditions.

3. The raw material of the substrate material is wood with abundant reserves, low cost and environmental protection, and the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The production cost of the N electrocatalytic material is low.

Therefore, the method has the characteristics of simple process, low cost and environmental friendliness, and the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The N electrocatalytic material can stabilize electrolyzed water under acidic and alkaline conditions.

Drawings

FIG. 1 shows a wood-based porous activated carbon/Ni prepared according to the present invention_0.2Mo_0.8SEM photograph of N electrocatalytic material;

FIG. 2 shows the wood-based porous activated carbon/Ni shown in FIG. 1_0.2Mo_0.8An electro-catalytic hydrogen evolution LSV curve diagram of the N electro-catalytic material under an acidic condition;

FIG. 3 is the wood-based porous activated carbon/Ni shown in FIG. 1_0.2Mo_0.8An electro-catalytic oxygen evolution LSV curve diagram of the N electro-catalytic material under an acidic condition;

FIG. 4 is the wood-based porous activated carbon/Ni shown in FIG. 1_0.2Mo_0.8And (3) a full hydrolysis stability test chart of the N electro-catalytic material under an acidic condition.

Detailed Description

The invention is further described with reference to the following figures and detailed description, without limiting its scope.

Wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material and a preparation method thereof. The preparation method comprises the following steps:

cutting the wood into blocks, washing the blocks with deionized water for 2-3 times, and drying the blocks at the temperature of 55-65 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block into 3-5 parts by mass of 15-30 wt% ZnCl₂Treating the wood blocks in the solution at 105-115 ℃ for 45-50 hours to obtain wood blocks treated by zinc chloride; and (3) carrying out heat treatment on the wood blocks treated by the zinc chloride for 2-4 hours under the conditions of high-purity argon atmosphere and 800-900 ℃, washing with deionized water for 3-4 times, and drying to obtain the wood-based porous activated carbon material.

Step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 1-2 parts by mass of NiCl₂·6H₂Adding O into 97-98 parts by mass of deionized water, and stirring for 10-20 minutes to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 3-5 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 150-170 ℃ for 5-7 hours, naturally cooling to room temperature, taking out, washing with deionized water for 2-3 times, and drying for 24-48 hours to obtain wood-based porous activated carbon/NiMoO₄A material.

Step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is subjected to heat treatment for 10-30 minutes under the conditions of ammonia atmosphere and 550-650 ℃ to prepare the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

The wood is one of poplar, pine, basswood, bamboo, sapelli wood and maple wood.

The length, width and height of the wood block are (30-40) x (10-20) x (5-10) mm.

In this embodiment:

the purity of the high-purity argon is more than 99.999 percent;

the purity of the ammonia gas is more than 99.6 percent.

The detailed description is omitted in the embodiments.

Example 1

Wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:

cutting wood into blocks, washing the blocks for 2 times by using deionized water, and drying the blocks at the temperature of 55 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block in 5 parts by mass of 15 wt% ZnCl₂Treating the wood blocks in the solution at 105 ℃ for 45 hours to obtain wood blocks treated by zinc chloride; and (3) carrying out heat treatment on the wood blocks treated by the zinc chloride for 2 hours in a high-purity argon atmosphere at 800 ℃, washing with deionized water for 3 times, and drying to obtain the wood-based porous activated carbon material.

Step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 1 part by mass of NiCl₂·6H₂Adding O into 98 parts by mass of deionized water, and stirring for 10 minutes to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 3 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 150 ℃ for 5 hours, naturally cooling to room temperature, taking out, washing with deionized water for 2 times, and drying for 24 hours to obtain wood-based porous activated carbon/NiMoO₄A material.

Step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is thermally treated for 10 minutes under the conditions of ammonia atmosphere and 550 ℃, and the wood-based porous activated carbon/Ni is prepared_0.2Mo_0.8An N electrocatalytic material.

In this embodiment: the wood is basswood; the length × width × height of the block is 40 × 20 × 10 mm.

Example 2

Wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material and a preparation method thereof. The preparation method is characterized by comprising the following steps:

cutting wood into blocks, washing the blocks with deionized water for 3 times, and drying the blocks at the temperature of 60 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block in 4 parts by mass of 20 wt% ZnCl₂In solution, in 11Treating at 0 deg.C for 48 hr to obtain wood blocks treated with zinc chloride; and (3) carrying out heat treatment on the wood blocks treated by the zinc chloride for 3 hours under the conditions of high-purity argon atmosphere and 850 ℃, washing for 3 times by using deionized water, and drying to obtain the wood-based porous activated carbon material.

Step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 1.5 parts by mass of NiCl₂·6H₂Adding O into 97.5 parts by mass of deionized water, and stirring for 15 minutes to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 4 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 160 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water for 2 times, and drying for 36 hours to obtain wood-based porous activated carbon/NiMoO₄A material.

Step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is thermally treated for 20 minutes under the conditions of ammonia atmosphere and 600 ℃ to prepare the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

In this embodiment: the wood is one of pine, poplar and sapelli wood; the length × width × height of the block is 35 × 15 × 8 mm.

Example 3

Wood-based porous activated carbon/Ni_0.2Mo_0.8N electrocatalytic material and a preparation method thereof. The preparation method is characterized by comprising the following steps:

cutting wood into blocks, washing the blocks for 2 times by using deionized water, and drying the blocks at the temperature of 65 ℃ to obtain pretreated wood blocks; dipping 1 part by mass of the pretreated wood block in 3 parts by mass of 30 wt% ZnCl₂Treating the wood blocks in the solution at 115 deg.C for 50 hr to obtain wood blocks treated with zinc chloride; and (3) carrying out heat treatment on the wood blocks treated by the zinc chloride for 4 hours under the conditions of high-purity argon atmosphere and 900 ℃, washing for 4 times by using deionized water, and drying to obtain the wood-based porous activated carbon material.

Step two, adding 1 part by mass of Na₂MoO₄·2H₂O and 2 parts by mass of NiCl₂·6H₂O is added to 97 massStirring the mixture for 20 minutes in the deionized water to obtain a mixed solution; adding the mixed solution into a hydrothermal reaction kettle, adding 5 parts by mass of the wood-based porous activated carbon material, carrying out heat treatment at 170 ℃ for 7 hours, naturally cooling to room temperature, taking out, washing with deionized water for 3 times, and drying for 48 hours to obtain the wood-based porous activated carbon/NiMoO₄A material.

Step three, carrying out porous activated carbon/NiMoO on the wood head base₄The material is thermally treated for 30 minutes under the condition of ammonia atmosphere and 650 ℃ to prepare the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material.

In this embodiment: the wood is bamboo or maple; the length × width × height of the block is 30 × 10 × 5 mm.

Compared with the prior art, the specific implementation mode has the following advantages:

1. in the specific embodiment, the pretreated wood block is dipped in ZnCl₂In the solution, performing heat treatment in a high-purity argon atmosphere at 800-900 ℃ to obtain a wood-based porous activated carbon material; then adding Na₂MoO₄·2H₂O、NiCl₂·6H₂Adding a mixed solution of O and deionized water into a hydrothermal reaction kettle, adding a wood-based porous activated carbon material for hydrothermal reaction, and finally carrying out heat treatment in an ammonia atmosphere at 550-650 ℃ to obtain the wood-based porous activated carbon/Ni_0.2Mo_0.8An N electrocatalytic material. The specific implementation mode does not need to use a surfactant, has simple process, saves the production cost and is environment-friendly.

2. Wood-based porous activated carbon/Ni prepared according to this embodiment_0.2Mo_0.8The N electrocatalytic material is shown in the attached figure: FIG. 1 is a wood-based porous activated carbon/Ni prepared in example 1_0.2Mo_0.8SEM photograph of N electrocatalytic material; FIG. 2 shows the wood-based porous activated carbon/Ni shown in FIG. 1_0.2Mo_0.8An electro-catalytic hydrogen evolution LSV curve diagram of the N electro-catalytic material under an acidic condition; FIG. 3 is the wood-based porous activated carbon/Ni shown in FIG. 1_0.2Mo_0.8An electro-catalytic oxygen evolution LSV curve diagram of the N electro-catalytic material under an acidic condition; FIG. 4Is wood-based porous activated carbon/Ni shown in figure 1_0.2Mo_0.8And (3) a full hydrolysis stability test chart of the N electro-catalytic material under an acidic condition. As can be seen from FIG. 1, the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8A large amount of one-dimensional Ni with the size of 5-10 mu m exists in the N electro-catalysis material_0.2Mo_0.8The N micron lines grow on the wood-based porous activated carbon; as can be seen from fig. 2: at a current density of 10mA cm^-2The prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The electrocatalytic hydrogen evolution overpotential of the N electrocatalytic material is 23.7 mV; as can be seen from fig. 3: at a current density of 50mA cm^-2The prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The electrocatalytic oxygen evolution overpotential of the N electrocatalytic material is 455 mV; as can be seen from fig. 4: when the applied voltage is 1.7V, the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The N electrocatalytic material can stabilize electrolyzed water under acidic conditions. Namely, the base material is wood-based porous activated carbon material, so that the electrolytic water is strong in corrosion resistance and cannot be corroded by acid or alkali, and therefore, the electrolytic water can be stably electrolyzed under acidic and alkaline conditions.

3. The base material of the embodiment is wood with abundant reserves, low cost and environmental protection, so the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The production cost of the N electrocatalytic material is low.

Therefore, the specific implementation mode has the characteristics of simple process, low cost and environmental friendliness, and the prepared wood-based porous activated carbon/Ni_0.2Mo_0.8The N electrocatalytic material can stabilize electrolyzed water under acidic and alkaline conditions.