阅读说明：本技术 用于电催化全解水的金属掺杂二硫化铼纳米片阵列的制备方法 (The preparation method of metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water ) 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 2019-07-15 设计创作，主要内容包括：本发明涉及一种用于电催化全解水的金属掺杂二硫化铼纳米片阵列的制备方法,包括下列步骤：将六水合硝酸盐、高铼酸铵、盐酸羟胺和硫脲,溶入去离子水,形成混合溶液；将上述混合溶液转移到高压釜中,将一片酸处理过的碳布浸入混合溶液中,置于200-230℃的烘箱中,保温一段时间。将高压釜自然冷却至室温,取出载满样品的碳布,清洗干净后干燥处理,得到产物金属掺杂二硫化铼纳米片阵列M-ReS<Sub>2</Sub>/CC。所述的方法制备的M-ReS<Sub>2</Sub>/CC应用于HER电催化剂。(The present invention relates to a kind of preparation methods of metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water, including the following steps: by six nitric hydrate salt, ammonium perrhenate, hydroxylamine hydrochloride and thiocarbamide, dissolves in deionized water, forms mixed solution；Above-mentioned mixed solution is transferred in autoclave, the processed carbon cloth of a piece of acid is immersed in mixed solution, is placed in 200-230 DEG C of baking oven, heat preservation a period of time.By autoclave cooled to room temperature, the carbon cloth for being loaded with sample is taken out, is dried after cleaning up, obtains product metal doping rhenium disulfide nano-chip arrays M-ReS 2 /CC.The M-ReS of the method preparation 2 / CC is applied to HER elctro-catalyst.)

1. a kind of preparation method of the metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water, including following step It is rapid:

(1) is (1~5) according to molar ratio: 10:30:45's by six nitric hydrate salt, ammonium perrhenate, hydroxylamine hydrochloride and thiocarbamide Proportion dissolves in deionized water, forms mixed solution.

(2) above-mentioned mixed solution is transferred in autoclave by, and the processed carbon cloth of a piece of acid is immersed in mixed solution, is placed in In 200-230 DEG C of baking oven, heat preservation a period of time.

(3) autoclave cooled to room temperature is taken out the carbon cloth for being loaded with sample, is dried after cleaning up, obtains product by Metal-doped rhenium disulfide nano-chip arrays M-ReS₂/CC。

2. the method according to claim 1, wherein the six nitric hydrate salt are Nickelous nitrate hexahydrate, six One of nitric hydrate cobalt, six nitric hydrate iron, manganese nitrate hexahydrate, six nitric hydrate copper or zinc nitrate or mixture.

3. the M-ReS of method preparation described in claim 1₂/ CC is applied to HER elctro-catalyst.

Technical field

The invention belongs to electro-catalysis technical fields, and in particular to the metal-doped modified rhenium disulfide nano-chip arrays of one kind Preparation method.

Background technique

Hydrogen is ideal clean energy resource carrier, and electrocatalytic decomposition water is a kind of low cost and the clean side for obtaining hydrogen energy source Formula.Electrocatalytic decomposition water include cathode hydrogen evolution reaction (HER) and Oxygen anodic evolution react (OER) two half-reactions, however liberation of hydrogen with The overpotential of oxygen evolution reaction is higher, it is therefore necessary to have efficient, stable elctro-catalyst to be just able to achieve.Currently used for elctro-catalyst There are still it is expensive, have a single function, catalytic activity is low, stability is poor the disadvantages of, seriously constrain water electrolysis method hydrogen producing technology Development, therefore be badly in need of developing low-cost, difunctional, high activity, high stability material solve the problems, such as this.

There is low in cost, edge site to urge for the discovery of two-dimensional layer transition metal dichalcogenide (TMDs) nano material Change active high feature, highly asymmetric 1T ' phase TMDs material-ReS₂It is proved to have by researcher and is better than 1T phase and 2H The characteristics of phase electric conductivity and stability.ReS₂Unique weak coupling effect can not only promote electrolyte ion in the expansion of interlayer It dissipates, and more marginal positions and datum level can be exposed, optimal electrocatalysis characteristic is reached as activated centre.It is existing Stage is to ReS₂The research of elctro-catalyst concentrates on HER reaction, does not study OER and reacts relevant work, this is because transition The intermediate product adsorption capacity that metal disulfides react OER is too low.It is found by consulting literatures, Ni, Fe base OER catalyst It is one of the potential candidate for being expected to substitution noble metal catalyst at this stage, inherent shortcoming caused by containing transition metal element can To promote intermediate product in the absorption of catalyst surface.Therefore it is lacked it is proposed that being introduced using transition metal element doped method It falls into, regulates and controls ReS₂Electronic structure and intermediate product in the suction-operated of catalyst surface, there is it under alkaline condition Good electro-catalysis OER performance prepares the difunctional complete solution water catalyst of the electro-catalysis haveing excellent performance.

Summary of the invention

The object of the present invention is to provide a kind of metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water Preparation method directly grows the nano-chip arrays of metal-doped rhenium disulfide in carbon cloth surfaces, and it is complete to be used for electro-catalysis Xie Shui reaction.The material is that metal (M=Fe, Co, Ni, Mn, Cu, Zn) adulterates ReS₂Nano-chip arrays are grown on carbon cloth, system Standby process is simple, as difunctional complete solution water power catalyst, has good chemical property.The method that the present invention uses has Good universality is suitable for most of transition metal, and preparation process is simple, time-consuming short, and the electricity that rhenium disulfide can be improved is urged Change performance.Technical scheme is as follows:

A kind of preparation method of the metal-doped rhenium disulfide nano-chip arrays for electro-catalysis complete solution water, including following step It is rapid:

(1) is (1~5): 10:30 according to molar ratio by six nitric hydrate salt, ammonium perrhenate, hydroxylamine hydrochloride and thiocarbamide: 45 proportion dissolves in deionized water, forms mixed solution.

(2) above-mentioned mixed solution is transferred in autoclave by, and the processed carbon cloth of a piece of acid is immersed in mixed solution, It is placed in 200-230 DEG C of baking oven, heat preservation a period of time.

(3) autoclave cooled to room temperature is taken out the carbon cloth for being loaded with sample, is dried, obtains after cleaning up by Product metal adulterates rhenium disulfide nano-chip arrays M-ReS₂/CC。

The six nitric hydrate salt are Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate, six nitric hydrate iron, six nitric hydrates One of manganese, six nitric hydrate copper or zinc nitrate or mixture.

The M-ReS of the method preparation₂/ CC can be applied to HER elctro-catalyst.

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

(1) the present invention directly grows metallic element doping rhenium disulfide in carbon cloth surfaces using the method for a step hydro-thermal Nano-chip arrays.This method has good universality, is suitable for most of transition metal, and preparation process is simple, time-consuming short.

(2) the present invention utilizes the method modified transition metal disulphide of metallic element doping, while improving rhenium disulfide Liberation of hydrogen, oxygen evolution reaction activity become efficient difunctional complete solution water power catalyst.

(3) for product growth in situ in carbon cloth surfaces, the self supporting structure prepared can carry out electro-catalysis directly as electrode Reaction, without adding expensive adhesive coated in glassy carbon electrode surface, preparation process is simple, reduces cost, exposes More active sites improve electro catalytic activity.

Detailed description of the invention

Fig. 1 is the Ni-ReS that the embodiment of the present invention 1 obtains₂The SEM photograph of/CC.From this view it is apparent that Ni-ReS₂/ CC is in Existing sheet pattern, Ni-ReS₂Nanometer sheet orients vertical-growth in carbon cloth surfaces.

Fig. 2 is the Ni-ReS that the embodiment of the present invention 1 obtains₂The XRD photo of/CC.From this view it is apparent that after adulterating Ni It is still ReS₂Object phase.

Fig. 3 is the Ni-ReS that the embodiment of the present invention 1 obtains₂The OER performance map of/CC.From this view it is apparent that elctro-catalyst Good electrocatalysis characteristic.

Fig. 4 is the Ni-ReS that the embodiment of the present invention 1 obtains₂The HER performance map of/CC.From this view it is apparent that elctro-catalyst Good electrocatalysis characteristic.

The present invention does not address place and is suitable for the prior art.

The specific embodiment of preparation method of the present invention is given below.Preparation that these embodiments are only used for that the present invention will be described in detail Method is not intended to limit the protection scope of the claim of this application.

Specific embodiment

The present invention prepares the efficiently difunctional complete solution of transient metal doped rhenium disulfide nanometer sheet with the method for a step hydro-thermal Water power catalyst.Here we are used as conductive current collector using carbon cloth (CC), and nitrate is as source metal, in surface vertical-growth Rhenium disulfide nano-chip arrays (the M-ReS of metal (M) doping out₂/ CC), wherein M can be Fe, Co, Ni, Mn, Cu, Zn.Through electricity Test chemical, Ni-ReS₂/ CC has fabulous HER and OER activity, and current density is 10mAcm in 1M KOH electrolyte^-2When HER overpotential is 110mV, and OER overpotential is 210mV.