CN115161694A - Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 Nanocluster heterojunction array and preparation method and application thereof - Google Patents

Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 Nanocluster heterojunction array and preparation method and application thereof Download PDF

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CN115161694A
CN115161694A CN202210834149.4A CN202210834149A CN115161694A CN 115161694 A CN115161694 A CN 115161694A CN 202210834149 A CN202210834149 A CN 202210834149A CN 115161694 A CN115161694 A CN 115161694A
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carbon fiber
fiber cloth
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杨勇
刘渊
尧慎曼
龚吴非
郭满满
俞挺
袁彩雷
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Jiangxi Normal University
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Abstract

The invention relates to the field of nano electro-catalytic materials, in particular to Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array and a preparation method and application thereof. The preparation method of the heterojunction array is easy to popularize, and only simple chemical solution reaction is combined with one-step low-temperature phosphating treatment. The Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 Nanocluster heterojunctionThe array comprises a carbon fiber cloth substrate and a heterojunction array grown on the surface of the carbon fiber cloth, wherein the heterojunction array is formed by doping CoP and Ni (PO) with Mn 3 ) 2 And (4) forming. Mn-doped CoP grows approximately vertically on a carbon fiber cloth substrate in the form of nanowires, and the surfaces of the nanowires are uniformly wrapped with Ni (PO) 3 ) 2 Nanoclusters. Thanks to the doping of Mn elements and the unique cobalt phosphide/phosphate heterointerface, such heterojunction arrays have excellent properties in electrocatalytic decomposition of water.

Description

Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 Nanocluster heterojunction array and preparation method and application thereof
Technical Field
The invention relates to the field of preparation and application of nano electro-catalytic materials, in particular to Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array and a preparation method and application thereof.
Background
With the explosive growth of the world population and the acceleration of industrialization, energy shortage has become a tripartite stone for further development of human society. Fossil energy, which is the main body of the world's energy structure, not only has insufficient reserves and uneven distribution, but also has significant environmental pollution problems. Therefore, the development of renewable clean energy (such as hydrogen energy) is urgent. Electrocatalytic decomposition of water has recently received much attention as an efficient and environmentally friendly method for producing hydrogen. Precious metal materials (especially platinum and ruthenium/iridium) are highly effective catalysts for electrocatalytic water splitting. However, they have great limitations in industrial use due to their scarce reserves and high cost. It has become a hot point of research to explore economical and efficient electrocatalysts and optimize the electrocatalysts performance. In recent years, transition metal oxides, sulfides, selenides, phosphides, and carbides have been developed successively. Among these catalysts, co-based phosphides (including CoP, co) 2 P and CoP 3 ) Because of the advantages of rich sources, good conductivity, rich oxidation-reduction sites and the like, the noble metal catalyst is considered to be a substitute with great competitiveness and prospect. However, the weak water dissociation process and the adsorption capacity for reaction intermediates are not goodThe electrocatalytic efficiency of cobalt-based phosphides is greatly limited, especially in alkaline electrolytes. Furthermore, due to the incompatibility of Hydrogen Evolution Reaction (HER) activity and Oxygen Evolution Reaction (OER) activity of cobalt-based phosphides in specific pH environments, achieving efficient overall water splitting in symmetric two-electrode systems remains a challenge.
To overcome the above inherent drawbacks of cobalt-based phosphides, it has become a common strategy to introduce a second or third phase of metallic elements to construct a bimetallic or trimetallic phosphide. It is reported that the introduction of the second phase or the third phase metal elements (such as Fe, ni, mo, cu, mn, etc.) can effectively optimize the surface electronic structure of the Co-based phosphide, so that the Co-based phosphide has more active centers, thereby improving the inherent electrocatalytic activity. Among various metallic elements used for doping cobalt-based phosphide, manganese (Mn) is particularly promising because it has higher electronegativity than most metallic elements, and it can greatly facilitate electron transport and adjust electron structure. However, current research on manganese-doped cobalt-based phosphides has focused primarily on powder material systems. Their electrocatalytic properties are still not ideal due to active center exposure and charge transfer capability limitations.
In addition to doping with metallic elements, the construction of a heterointerface by integrating different catalysts is another effective means to improve the electrocatalytic performance of Co-based phosphide catalysts. The result shows that abundant heterogeneous interfaces can not only expose more reaction sites and accelerate the electron transfer rate, but also realize the synchronous adsorption of reaction intermediates. However, in fact, due to weak interface interaction and mismatched energy band structures, in many cases, a dense and rich heterogeneous interface is difficult to form between two different catalysts, which makes it difficult for the carrier to realize effective transfer on the interface, and limits the full exertion of the efficiency of the heterogeneous interface. Therefore, the search for co-based phosphide heterostructures with dense, rich heterointerfaces remains a great challenge.
Disclosure of Invention
The invention aims to provide Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array and a preparation method thereof, aiming at solving the problems in the prior artThe water electrocatalytic decomposition efficiency of the cobalt-based phosphide is low.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
The Mn-doped CoP nanowire composite Ni (PO) provided by the invention 3 ) 2 The nano-cluster heterojunction array comprises a carbon fiber cloth substrate and a heterojunction array growing on the surface of the carbon fiber cloth; the heterojunction array is made of Mn-doped CoP and Ni (PO) 3 ) 2 And (4) forming. Mn-doped CoP grows on a carbon fiber cloth substrate approximately vertically in the form of nanowires, the diameters of the nanowires are 50-100 nm, the lengths of the nanowires are 1-5 mu m, and the surfaces of the nanowires are uniformly wrapped with Ni (PO) 3 ) 2 Nanoclusters, the nanoclusters being about 2nm in size.
Preferably, the substrate is a carbon fiber cloth.
The Mn-doped CoP nanowire composite Ni (PO) provided by the invention 3 ) 2 The preparation method of the nanocluster heterojunction array comprises the following steps:
before growth, firstly, ultrasonically washing a carbon fiber cloth substrate in acetone, deionized water and absolute ethyl alcohol in sequence to remove a surface oxide layer and organic matters;
step (2), growing a CoMn double hydroxide nanowire array on the surface of the carbon fiber cloth substrate by adopting a hydrothermal method; specifically, mn (NO) 3 ) 2 ·4H 2 O (manganese nitrate) and Co (NO) 3 ) 2 ·6H 2 O (cobalt nitrate hexahydrate), NH 4 F (ammonium fluoride) and urea in a molar ratio of 1: (1.5-3): (5-10): (10-20) are sequentially dissolved in 70-80 mL of deionized water to form a uniform solution under ultrasonic treatment; transferring the solution into a 100mL stainless steel autoclave, and obliquely inserting the cleaned carbon fiber cloth substrate into the solution; the autoclave is kept for 3 to 10 hours at the temperature of between 100 and 120 ℃; after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the carbon fiber cloth after being cleaned in an oven at 70 ℃ for 2-8 hours to obtain a CoMn double hydroxide nanowire array;
step (3) adopting a solvothermal method to prepare CoMn double hydroxide nanowire arraysCoating Ni (OH) on the surface of the column 2 Nanosheets, to obtain a composite hydroxide heterostructure array; specifically, mixing Ni (NO) 3 ) 2 ·6H 2 O (nickel nitrate hexahydrate) and Hexamethylenetetramine (HMT) in a molar ratio of 1: (5-10) dissolving in 30mL of ethanol to form a uniform solution, and transferring the uniform solution into a 100mL stainless steel autoclave; and (3) inserting the double hydroxide nanowire array obtained in the step (2) into the solution, and maintaining the high-pressure kettle at the temperature of 120-140 ℃ for 2-6 h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 2-8 hours to obtain the composite hydroxide heterostructure array.
Step (4), adopting a one-step low-temperature phosphating process to convert the composite hydroxide heterostructure array into a final product, namely Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array. Specifically, the composite hydroxide heterostructure array obtained in the step (3) and 0.5-1.5 g of sodium hypophosphite (NaH) 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, calcining the quartz boats in argon atmosphere at 300 ℃ for 1 to 4 hours to obtain Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
Preferably, in the step (2), mn (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 O、NH 4 The molar ratio of F to urea is 1:2:6:12.
preferably, in the step (3), ni (NO) 3 ) 2 ·6H 2 The molar ratio of O to Hexamethylenetetramine (HMT) is 1:8.7.
the Mn-doped CoP nanowire composite Ni (PO) provided by the invention 3 ) 2 The nanocluster heterojunction array can be used as a high-efficiency electrocatalyst for electrocatalytic water decomposition reaction.
The invention has the technical effects that: (1) The preparation method of the heterojunction array is easy to popularize, and only simple chemical solution reaction is combined with one-step low-temperature phosphating treatment; (2) Prepared phosphide/phosphate heterojunctions in array formThe carbon fiber substrate is arranged on the carbon fiber substrate, and has good charge transmission efficiency and rich heterogeneous interface contact; (3) The heterojunction array enables the product Mn doped CoP nanowire composite Ni (PO) 3 ) 2 The nanocluster heterojunction array has excellent performance in both electrocatalytic HER and OER.
Drawings
FIG. 1 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs of the nanocluster heterojunction array and the comparative sample.
FIG. 2 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 X-ray diffraction (XRD) patterns of the nanocluster heterojunction array and of the comparative sample.
FIG. 3 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Graph of electrocatalytic HER performance for the nanocluster heterojunction array and the comparative sample.
FIG. 4 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Plot of electrocatalytic OER performance for the nanocluster heterojunction array and the comparative sample.
Detailed Description
The technical solutions and advantages of the present invention will be described in detail below with reference to the accompanying drawings and specific examples, which are intended to help the reader to better understand the essence of the present invention, but should not be construed as limiting the scope of the present invention.
In the following examples, ni (PO) was composited in Mn-doped CoP nanowires 3 ) 2 Before the growth of the nanocluster heterojunction array, the carbon fiber cloth substrate required by growth is processed through the following steps: and ultrasonically washing the carbon fiber cloth substrate in acetone, deionized water and absolute ethyl alcohol in sequence to remove a surface oxide layer and organic matters.
Preparation example 1:
firstly, growing a CoMn double hydroxide nanowire array on the surface of a carbon fiber cloth substrate by adopting a hydrothermal method; specifically, mn (NO) 3 ) 2 ·4H 2 O,Co(NO 3 ) 2 ·6H 2 O,NH 4 F and urea are mixed according to a molar ratio of 1:2:6:12 were in turn dissolved in 80mL of deionized water to form a homogeneous solution under sonication. The solution was transferred to a 100mL stainless steel autoclave and the cleaned carbon fiber cloth substrate was then inserted into the solution diagonally. The autoclave was maintained at 100 ℃ for 5h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 8 hours to obtain the CoMn double hydroxide nanowire array. Secondly, coating Ni (OH) on the surface of the CoMn double hydroxide nanowire array by adopting a solvothermal method 2 Nanosheets; specifically, mixing Ni (NO) 3 ) 2 ·6H 2 O and Hexamethylenetetramine (HMT) in a molar ratio of 1:8.7 was dissolved in 30mL of ethanol to form a homogeneous solution, which was transferred to a 100mL stainless steel autoclave. The double hydroxide nanowire array obtained in the above step was then inserted into the solution and the autoclave was maintained at 120 ℃ for 4h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the washed carbon fiber cloth in an oven at 70 ℃ for 8 hours to obtain the composite hydroxide heterostructure array. Finally, converting the composite hydroxide heterostructure array into a final product by adopting a one-step low-temperature phosphating process; specifically, the composite hydroxide heterostructure array obtained in the above step and 1g of sodium hypophosphite (NaH) are mixed 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, calcining the quartz boats in argon atmosphere at 300 ℃ for 2 hours to obtain Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
Preparation example 2:
firstly, growing a CoMn double hydroxide nanowire array on the surface of a carbon fiber cloth substrate by adopting a hydrothermal method; specifically, mn (NO) 3 ) 2 ·4H 2 O,Co(NO 3 ) 2 ·6H 2 O,NH 4 F and urea are mixed according to a molar ratio of 1:2:6:12 were in turn dissolved in 70mL of deionized water to form a homogeneous solution under sonication. Transfer the solution to a 100mL stainless steel autoclaveAnd (4) obliquely inserting the cleaned carbon fiber cloth substrate into the solution in the kettle. The autoclave was maintained at 110 ℃ for 5h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 6 hours to obtain the CoMn double hydroxide nanowire array. Secondly, coating Ni (OH) on the surface of the CoMn double hydroxide nanowire array by adopting a solvothermal method 2 Nanosheets; specifically, mixing Ni (NO) 3 ) 2 ·6H 2 O and Hexamethylenetetramine (HMT) in a molar ratio of 1:8.7 was dissolved in 30mL of ethanol to form a homogeneous solution, which was transferred to a 100mL stainless steel autoclave. The double hydroxide nanowire array obtained in the above step was then inserted into the solution and the autoclave was maintained at 120 ℃ for 5h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 8 hours to obtain the composite hydroxide heterostructure array. Finally, converting the composite hydroxide heterostructure array into a final product by adopting a one-step low-temperature phosphating process; specifically, the composite hydroxide heterostructure array obtained in the above step and 1g of sodium hypophosphite (NaH) are mixed 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, calcining the quartz boats in argon atmosphere at 300 ℃ for 2 hours to obtain Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
Preparation example 3:
firstly, growing a CoMn double-hydroxide nanowire array on the surface of a carbon fiber cloth substrate by adopting a hydrothermal method; specifically, mn (NO) 3 ) 2 ·4H 2 O,Co(NO 3 ) 2 ·6H 2 O,NH 4 F and urea are mixed according to a molar ratio of 1:2:6:12 were in turn dissolved in 70mL of deionized water to form a homogeneous solution under sonication. The solution was transferred to a 100mL stainless steel autoclave and the cleaned carbon fiber cloth substrate was then inserted into the solution diagonally. The autoclave was maintained at 100 ℃ for 6h. After the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally cleaning the carbon fiber cloth after washingAnd drying in an oven at 70 ℃ for 5 hours to obtain the CoMn double hydroxide nanowire array. Secondly, coating Ni (OH) on the surface of the CoMn double hydroxide nanowire array by adopting a solvothermal method 2 Nanosheets; specifically, mixing Ni (NO) 3 ) 2 ·6H 2 O and Hexamethylenetetramine (HMT) in a molar ratio of 1:8.7 was dissolved in 30mL of ethanol to form a homogeneous solution, which was transferred to a 100mL stainless steel autoclave. The double hydroxide nanowire array obtained in the above step was then inserted into the solution and the autoclave was maintained at 130 ℃ for 5h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the washed carbon fiber cloth in an oven at 70 ℃ for 6 hours to obtain the composite hydroxide heterostructure array. Finally, adopting a one-step low-temperature phosphating process to convert the composite hydroxide heterostructure array into a final product; specifically, the composite hydroxide heterostructure array obtained in the above step and 1g of sodium hypophosphite (NaH) are mixed 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, calcining the quartz boats in argon atmosphere at 300 ℃ for 2 hours to obtain Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
In the materials prepared in preparation examples 1 to 3, mn-doped CoP is approximately vertically grown on a carbon fiber cloth substrate in the form of nanowires, the diameter of each nanowire is 50 to 100nm, the length of each nanowire is 1 to 5 mu m, and the surface of each nanowire is uniformly wrapped with Ni (PO) 3 ) 2 Nanoclusters, the nanoclusters being about 2nm in size.
In order to prove the Mn-doped CoP nanowire composite Ni (PO) prepared by the method 3 ) 2 The unique advantages of the nanocluster heterojunction array in the field of electrocatalysis are that two comparative materials are synthesized by a similar method, namely a Mn-doped CoP nanowire array and a Ni (PO) nanowire array 3 ) 2 Nanoclusters.
Preparation of comparative example:
the carbon fiber cloth substrate required for growth is processed by the following steps: and ultrasonically washing the carbon fiber cloth substrate in acetone, deionized water and absolute ethyl alcohol in sequence to remove a surface oxide layer and organic matters.
The preparation of the comparative material Mn doped CoP nanowire array is completed according to the following steps: firstly, growing a CoMn double hydroxide nanowire array on the surface of a carbon fiber cloth substrate by adopting a hydrothermal method; specifically, mn (NO) 3 ) 2 ·4H 2 O,Co(NO 3 ) 2 ·6H 2 O,NH 4 F and urea are mixed according to a molar ratio of 1:2:6:12 were in turn dissolved in 80mL of deionized water to form a homogeneous solution under sonication. The solution was transferred to a 100mL stainless steel autoclave and the cleaned carbon fiber cloth substrate was then inserted diagonally into the solution. The autoclave was maintained at 100 ℃ for 5h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 8 hours to obtain the CoMn double hydroxide nanowire array. And secondly, converting the CoMn double hydroxide nanowire array into a final product Mn-doped CoP nanowire array by adopting a one-step low-temperature phosphating process. Specifically, 1g of sodium hypophosphite (NaH) and CoMn double hydroxide nanowire array obtained in the above step 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, setting the temperature of the quartz boats in argon atmosphere to 300 ℃ and calcining the quartz boats for 2 hours to obtain the comparison material Mn doped CoP nanowire array.
Comparative material Ni (PO) 3 ) 2 The preparation of the nanocluster is completed according to the following steps: firstly, adopting a solvothermal method to grow Ni (OH) on the surface of a carbon fiber cloth substrate 2 Nanosheets; specifically, mixing Ni (NO) 3 ) 2 ·6H 2 O and Hexamethylenetetramine (HMT) in a molar ratio of 1:8.7 was dissolved in 30mL of ethanol to form a homogeneous solution, which was transferred to a 100mL stainless steel autoclave. The carbon fiber cloth substrate was then inserted into the solution and the autoclave was maintained at 120 ℃ for 4h. And after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven for 8 hours at 70 ℃. Secondly, adopting a one-step low-temperature phosphating process to remove Ni (OH) 2 Conversion of nanosheets to Ni (PO) 3 ) 2 Nanoclusters; specifically, ni (OH) 2 Nano-sheetAnd 1g sodium hypophosphite (NaH) 2 PO 2 ) Respectively placing the quartz boats in a tube furnace, calcining the quartz boats in argon atmosphere at 300 ℃ for 2 hours to obtain a comparative material Ni (PO) 3 ) 2 Nanoclusters.
The Mn-doped CoP nanowire composite Ni (PO) prepared by the method 3 ) 2 The nanocluster heterojunction array can be used as an electrocatalyst for electrocatalytic water splitting reactions. Compounding the Mn-doped CoP nanowire with Ni (PO) 3 ) 2 The electrocatalytic HER and OER performances of the nanocluster heterojunction array and the two comparative materials are tested, and the test technical scheme is as follows: the electrocatalytic performance was tested using a three-electrode system of an electrochemical workstation. The counter electrode adopts a graphite rod electrode, and the reference electrode adopts a saturated calomel electrode. The heterojunction array grown on the carbon fiber cloth substrate was cut into 3mm × 3mm and used as a working electrode for testing. A1M KOH aqueous solution was used as an electrolyte. The polarization curve was measured using linear sweep voltammetry with a sweep rate set at 0.002V/s. All measured potentials were converted to reversible hydrogen electrode potentials.
FIG. 1 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs of the nanocluster heterojunction array and of the comparative sample. As can be seen from (a) to (c) of fig. 1, a uniform Mn-doped CoP nanowire array with a length of several micrometers and a diameter of about 50 to 100nm is densely grown on a carbon fiber cloth substrate. The high-resolution TEM image clearly observed a lattice fringe with a interplanar spacing of 0.284nm (as shown in FIG. 1 (d)), corresponding to the {011} crystallographic plane of the orthogonal phase CoP. In FIG. 1, (e) - (g) are Mn doped CoP nanowire composite Ni (PO) 3 ) 2 Morphological images of nanocluster heterojunction arrays. It can be found that nanoclusters with the size of about 2nm are uniformly wrapped on the surface of the nanowire to form a compact core-shell heterostructure. From the high-resolution TEM image shown in FIG. 1 (h), two lattice fringes with interplanar spacings of 0.208nm and 0.216nm, respectively, corresponding to the (210) plane of CoP and Ni (PO), respectively, can be observed 3 ) 2 The (411) crystal plane of (1). In conclusion, by means of a simple low-temperature phosphating treatment, simultaneous performance is possibleManganese doping and surface phosphate compounding are performed. The element mapping image shown in (i) in FIG. 1 can show that the Mn-doped CoP nanowire composite Ni (PO) prepared by the invention 3 ) 2 The elements of the nanocluster heterojunction array are uniformly distributed.
FIG. 2 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 An X-ray diffraction (XRD) pattern of the nanocluster heterojunction array and of the control sample; wherein (a) is Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 X-ray diffraction (XRD) pattern of the nanocluster heterojunction array, (b) X-ray diffraction (XRD) pattern of Mn-doped CoP nanowire array of the comparison sample, and (c) Ni (PO) of the comparison sample 3 ) 2 X-ray diffraction (XRD) pattern of the nanoclusters. From the spectrum, the characteristic peaks of the comparative material Mn doped CoP nanowire array are respectively located at 31.8 degrees, 36.3 degrees, 46.2 degrees, 48.1 degrees and 56.7 degrees, and respectively correspond to the (011), (111), (112), (211) and (301) crystal planes of the orthorhombic CoP standard card (JCPDS No. 29-0497), which indicates that the introduction of Mn does not form a new phase. Comparative material Ni (PO) 3 ) 2 Characteristic peak of nanocluster and monoclinic phase Ni (PO) 3 ) 2 Consensus (JCPDS No. 28-0708). A strong peak around 26 ° corresponds to the carbon fiber cloth substrate. Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 XRD peaks of the nanocluster heterojunction array show both orthorhombic CoP and monoclinic Ni (PO) 3 ) 2 Indicating the formation of a heterostructure.
FIG. 3 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Graph of electrocatalytic HER performance for the nanocluster heterojunction array and the comparative samples. As can be seen, mn-doped CoP nanowire composite Ni (PO) 3 ) 2 The performance of the nanocluster heterojunction array is obviously superior to that of a comparative material Mn doped CoP nanowire array and that of a comparative material Ni (PO) 3 ) 2 Nanoclusters at current densities of 10 and 20mA/cm 2 In time, mn doped CoP nanowire composite Ni (PO) 3 ) 2 The overpotential values for the nanocluster heterojunction array were 116 and 130mV, respectively, significantly lower than the control material. The excellent performance comes from the synergy of Mn doping and heterojunction recombinationHas the same effect.
FIG. 4 shows Mn doped CoP nanowire composite Ni (PO) prepared by the present invention 3 ) 2 Plot of electrocatalytic OER performance for the nanocluster heterojunction array and the comparative sample. It can be seen that Mn-doped CoP nanowire is compounded with Ni (PO) 3 ) 2 The current density of the nanocluster heterojunction array is 10mA/cm 2 The overpotential value (245 mV) was significantly lower than the control material, indicating that it had more excellent OER performance.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (8)

1. Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 The nano-cluster heterojunction array is characterized by comprising a carbon fiber cloth substrate and a heterojunction array growing on the surface of the carbon fiber cloth; the heterojunction array is formed by Mn-doped CoP and Ni (PO) 3 ) 2 Forming; mn-doped CoP grows on a carbon fiber cloth substrate approximately vertically in the form of nanowires, the diameter is 50-100 nm, the length is 1-5 mu m, and the surfaces of the nanowires are uniformly wrapped with Ni (PO) 3 ) 2 Nanoclusters, the nanoclusters being about 2nm in size.
2. The Mn-doped CoP nanowire composite Ni (PO) of claim 1 3 ) 2 The preparation method of the nanocluster heterojunction array is characterized by comprising the following steps of: firstly, growing a CoMn double-hydroxide nanowire array on the surface of a carbon fiber cloth substrate by adopting a hydrothermal method; then adopting a solvothermal method to wrap Ni (OH) on the surface of the CoMn double hydroxide nanowire array 2 Nanosheets, i.e. Ni (NO) 3 ) 2 ·6H 2 Dissolving O and hexamethylenetetramine in ethanol to form a uniform solution, transferring the solution and the CoMn double hydroxide nanowire array to a stainless steel autoclave for reaction, and obtaining a composite materialAn array of synthetic hydroxide heterostructures; finally, respectively placing the obtained composite hydroxide heterostructure array and sodium hypophosphite in a quartz boat by adopting a one-step low-temperature phosphating process, and then placing the quartz boat in a tube furnace to be calcined and converted into a final product under the argon atmosphere, namely Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
3. The preparation method of claim 2, wherein the specific steps of growing the CoMn double hydroxide nanowire array on the surface of the carbon fiber cloth substrate by a hydrothermal method are as follows: mixing Mn (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 O、NH 4 F and urea are mixed according to a molar ratio of 1: (1.5-3): (5-10): (10-20) are sequentially dissolved in 70-80 mL of deionized water to form a uniform solution under ultrasonic treatment; transferring the solution into a 100mL stainless steel autoclave, and obliquely inserting the cleaned carbon fiber cloth substrate into the solution; the autoclave is kept for 3 to 10 hours at the temperature of between 100 and 120 ℃; and after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 2-8 hours to obtain the CoMn double hydroxide nanowire array.
4. The preparation method according to claim 2, wherein the specific steps for obtaining the composite hydroxide heterostructure array by the solvothermal method are as follows: mixing Ni (NO) 3 ) 2 ·6H 2 O and hexamethylenetetramine in a molar ratio of 1: (5-10) dissolving in 30mL of ethanol to form a uniform solution, and transferring the uniform solution into a 100mL stainless steel autoclave; then inserting the obtained CoMn double hydroxide nanowire array into the solution, and keeping the high-pressure kettle at 120-140 ℃ for 2-6 h; and after the reaction is finished, taking out the carbon fiber cloth, alternately cleaning the carbon fiber cloth by using deionized water and absolute ethyl alcohol, and finally drying the cleaned carbon fiber cloth in an oven at 70 ℃ for 2-8 hours to obtain the composite hydroxide heterostructure array.
5. The preparation method according to claim 2, wherein the one-step low-temperature phosphating process comprises the following specific steps: respectively placing the obtained composite hydroxide heterostructure array and 0.5-1.5 g of sodium hypophosphite in a quartz boat, placing the quartz boat in a tube furnace, and calcining for 1-4 hours at 300 ℃ in an argon atmosphere to obtain Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 A nanocluster heterojunction array.
6. The method according to claim 3, wherein Mn (NO) 3 ) 2 ·4H 2 O、 Co(NO 3 ) 2 ·6H 2 O、NH 4 The molar ratio of F to urea is 1:2:6:12.
7. the method according to claim 4, wherein Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O to hexamethylenetetramine is 1:8.7.
8. the Mn-doped CoP nanowire composite Ni (PO) according to claim 1 3 ) 2 The application of the nanocluster heterojunction array in the aspect of electrocatalytic decomposition of water is characterized in that the heterojunction array material can be used as an electrocatalyst for HER and OER reactions.
CN202210834149.4A 2022-07-14 2022-07-14 Mn-doped CoP nanowire composite Ni (PO) 3 ) 2 Nanocluster heterojunction array and preparation method and application thereof Pending CN115161694A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115786932A (en) * 2022-12-09 2023-03-14 广西民族大学 Preparation method of carbon-coated manganese-doped CoP bifunctional decomposition water electrode

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115786932A (en) * 2022-12-09 2023-03-14 广西民族大学 Preparation method of carbon-coated manganese-doped CoP bifunctional decomposition water electrode

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