阅读说明：本技术 用于电催化析氢的钴掺杂二硫化铼纳米片阵列的制备方法 (Preparation method of cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution ) 是由 何芳 孙巧稚 赵乃勤 师春生 何春年 刘恩佐 马丽颖 沙军威 于 2019-07-01 设计创作，主要内容包括：本发明涉及一种用于电催化析氢的钴掺杂二硫化铼纳米片阵列的制备方法,包括下列步骤：将2-甲基咪唑水溶液加入到六水合硝酸钴的水溶液中将一片酸处理过的碳布浸入混合溶液中；反应一段时间后,取样品,用去离子水清洗；在同一溶液中再一段时间的生长得到ZIF-67纳米阵列样品,命名为ZIF-67/CC,最后,样品清洗后,干燥处理。将六水合硝酸钴溶于超纯水与乙醇的混合溶液中,将制备好的ZIF-67/CC放入其中进行水解,得到产物氢氧化钴纳米阵列Co(OH)<Sub>2</Sub>/CC；得到产物Co-ReS<Sub>2</Sub>/CC。所述的制备方法制得的Co-ReS<Sub>2</Sub>/CC应用于HER电催化剂。(The invention relates to a preparation method of a cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution, which comprises the following steps: adding 2-methylimidazole aqueous solution into cobalt nitrate hexahydrate aqueous solution, and immersing an acid-treated carbon cloth into the mixed solution; after reacting for a period of time, taking a sample, and cleaning the sample with deionized water; and growing in the same solution for a period of time to obtain a ZIF-67 nano array sample named ZIF-67/CC, and finally, cleaning the sample and drying. Dissolving cobalt nitrate hexahydrate in a mixed solution of ultrapure water and ethanol, and putting the prepared ZIF-67/CC into the mixed solution for hydrolysis to obtain a product cobalt hydroxide nano array Co (OH) 2/CC; the product Co-ReS2/CC is obtained. The Co-ReS2/CC prepared by the preparation method is applied to HER electrocatalysts.)

1. A preparation method of a cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution comprises the following steps:

(1) Adding an aqueous solution of 2-methylimidazole to an aqueous solution of cobalt nitrate hexahydrate in a molar ratio of Co (NO3) 2.6H 2O: 2-MIM (1: 14-1: 18), and immersing a piece of acid-treated carbon cloth into the mixed solution; after reacting for a period of time, taking a sample, and cleaning the sample with deionized water; and growing in the same solution for a period of time to obtain a ZIF-67 nano array sample named ZIF-67/CC, and finally, cleaning the sample and drying.

(2) Dissolving cobalt nitrate hexahydrate in a mixed solution of ultrapure water and ethanol, and putting the ZIF-67/CC prepared in the step (1) into the mixed solution for hydrolysis to obtain a product, namely a cobalt hydroxide nano array Co (OH) 2/CC.

(3) Dissolving ammonium perrhenate, hydroxylamine hydrochloride and thiourea into deionized water according to the molar ratio of NH4ReO4: HONH3Cl: CH4N2S of 1:3: 4.5-2: 3:4.5, transferring into a high-pressure kettle, placing Co (OH)2/CC prepared in the step (2) into the high-pressure kettle, and preserving the heat for a period of time in an oven at the temperature of 180-220 ℃ to obtain a product Co-ReS 2/CC.

2. The production method according to claim 1,

The Co-ReS2/CC prepared by the preparation method of claim 1 is applied to HER electrocatalyst.

Technical Field

The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a cobalt hydroxide nano array modified rhenium disulfide nanosheet loaded on carbon cloth.

background

In order to solve the increasing energy demand and environmental pressure in the process of human continuing development, the electrocatalytic hydrogen production technology is well paid attention by researchers due to the advantages of cleanness, low price and sustainability. The existing electrode material for water electrolysis has the defects of high price, small specific surface area, low electrocatalytic activity and the like, so that the potential is too high, the energy consumption is too large, the development of a water electrolysis hydrogen production technology is seriously restricted, and the development of a material which can produce hydrogen efficiently and has low price is urgently needed to solve the problem.

Rhenium disulfide (ReS2) is a two-dimensional (2D) group VII Transition Metal Disulfide (TMD) with a large number of active sites at the edge, and shows the potential of a high-performance catalyst in an energy conversion and storage device like a group VI isotropic TMD material, but rhenium disulfide nanosheets prepared by a common preparation method are difficult to directionally grow and easy to agglomerate, so that the activity of an electrocatalytic hydrogen evolution reaction is greatly reduced. The metal-organic framework (ZIF-67) is often used as an electrocatalyst or a precursor and a template for preparing the electrocatalyst due to excellent physicochemical properties of porosity, various structures, controllable chemical compositions and the like, and metal atoms are introduced in the preparation process, so that the electrocatalytic activity of the material can be greatly improved.

Disclosure of Invention

The invention aims to provide a preparation method of a cobalt-doped rhenium disulfide nanosheet array, the material is formed by growing Co-doped ReS2 on carbon cloth, the preparation process is simple, and the material has good electrochemical performance when used as a HER electrocatalyst. The technical scheme of the invention is as follows:

A preparation method of a cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution comprises the following steps:

(1) Adding an aqueous solution of 2-methylimidazole to an aqueous solution of cobalt nitrate hexahydrate in a molar ratio of Co (NO3) 2.6H 2O: 2-MIM (1: 14-1: 18), and immersing a piece of acid-treated carbon cloth into the mixed solution; after reacting for a period of time, taking a sample, and cleaning the sample with deionized water; and growing in the same solution for a period of time to obtain a ZIF-67 nano array sample named ZIF-67/CC, and finally, cleaning the sample and drying.

(2) Dissolving cobalt nitrate hexahydrate in a mixed solution of ultrapure water and ethanol, and putting the ZIF-67/CC prepared in the step (1) into the mixed solution for hydrolysis to obtain a product, namely a cobalt hydroxide nano array Co (OH) 2/CC.

(3) Dissolving ammonium perrhenate, hydroxylamine hydrochloride and thiourea into deionized water according to the molar ratio of NH4ReO4: HONH3Cl: CH4N2S of 1:3: 4.5-2: 3:4.5, transferring into a high-pressure kettle, placing Co (OH)2/CC prepared in the step (2) into the high-pressure kettle, and preserving the heat for a period of time in an oven at the temperature of 180-220 ℃ to obtain a product Co-ReS 2/CC.

The Co-ReS2/CC prepared by the preparation method is applied to HER electrocatalysts.

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

(1) The invention utilizes the ZIF-67 hydrolysate Co (OH)2 nano array as a template to grow the directionally vertical ReS2 nano sheet, exposes a large amount of active sites and improves the electro-catalytic hydrogen evolution performance.

(2) The invention utilizes ZIF-67 as a Co source to be doped into ReS2, and improves the hydrogen evolution reaction activity of ReS2 under alkaline conditions.

(3) The product grows on the surface of the carbon cloth in situ, the prepared self-supporting structure can be directly used as an electrode to carry out electrocatalytic hydrogen evolution reaction, and a high-price binder is not required to be added to coat the surface of the glassy carbon electrode, so that the preparation process is simple, the cost is reduced, more active sites are exposed, and the electrocatalytic activity is improved.

Drawings

FIG. 1 is an SEM photograph of Co-ReS2/CC obtained in example 1 of the present invention. The figure clearly shows that the Co-ReS2/CC presents lamellar morphology, and the ReS2 nanosheet grows on the surface of the carbon cloth in an oriented and vertical mode.

FIG. 2 is an XRD photograph of Co-ReS2/CC obtained in example 1 of the present invention. It is evident from this figure that the re 2 phase remains after Co doping.

FIG. 3 is a graph of the HER performance of Co-ReS2/CC obtained in example 1 of the present invention. The excellent catalytic performance of the electrocatalyst is evident from this figure.

Nothing in this specification is said to apply to the prior art.

Specific examples of the production method of the present invention are given below. These examples are only intended to illustrate the preparation process of the present invention in detail and do not limit the scope of protection of the claims of the present application.

Detailed Description