CN108264029A - A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials - Google Patents

A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials Download PDF

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CN108264029A
CN108264029A CN201810044276.8A CN201810044276A CN108264029A CN 108264029 A CN108264029 A CN 108264029A CN 201810044276 A CN201810044276 A CN 201810044276A CN 108264029 A CN108264029 A CN 108264029A
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杨东江
邹译慧
王克伟
佘希林
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Qingdao University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/08Other phosphides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C01INORGANIC CHEMISTRY
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    • C01P2004/03Particle morphology depicted by an image obtained by SEM
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/30Particle morphology extending in three dimensions
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials, which is characterized in that using CoNi double-metal hydroxides as presoma, three-dimensional flower-shaped CoP is obtained by the interior phosphatization of low-temperature short-time3And Ni2P two-phase composite nano materials.

Description

A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials
Technical field
The invention belongs to the preparation fields of nano material, and in particular to a kind of CoP3And Ni2The preparation of P two-phase composite materials Method and its application in terms of electro-catalysis hydrolyzes production hydrogen.
Background technology
Cleaning and regenerative resource there is an urgent need to pushed electrolysis aquatic products hydrogen catalyst exploration.Recently, transition metal Phosphide (TMP) is had proved to be with high activity, the HER catalyst of high stability, and not only in strongly acidic solution, And in for strong basicity and neutral medium, there is the faradic efficiency close to 100%.And with phosphorus content in phosphide Increase, electrocatalysis characteristic is better.Largely research shows that, nano hybrid can combine the excellent of each component as catalyst Point, and synergistic effect is generated in heterogeneous interface, greatly improve catalysis H2-producing capacity.Therefore the preparation of nano hybrid is more next More paid attention to by research staff.However traditional rich phosphorus compound preparation method is cumbersome, required phosphatization temperature is higher by (>=750 DEG C), time length (>=5h), obtained rich phosphorus compound is sintered substantially, and catalytic activity reduces.Therefore a kind of suitable rich phosphorus is found The preparation method of compound is most important.
Invention content
In order to overcome the drawbacks described above of the prior art, the present invention provides a kind of CoP3And Ni2The system of P two-phase composite materials Preparation Method.
A kind of CoP of the present invention3And Ni2The preparation method of P two-phase composite materials uses following technical scheme:
A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials, which is characterized in that with CoNi bimetal hydroxides Object is presoma, and three-dimensional flower-shaped CoP is obtained by the interior phosphatization of low-temperature short-time3And Ni2P two-phase composite nano materials.
A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials, includes the following steps:
(1) a certain amount of Co (NO3)2·6H2O, NiCl2·6H2Hydrothermal synthesis is spent under certain temperature in O and urea reaction kettle Shape CoNi duplex metal hydroxide nanometer pieces.
(2) sample for obtaining step (1) is placed in tube furnace with a certain amount of sodium hypophosphite and carries out phosphatization;
(3) samples with water and ethyl alcohol after phosphatization is taken to rinse repeatedly several times, is then dried.
Further, Co (NO in step (1)3)2·6H2O, NiCl2·6H2The adding proportion of O is that molecular weight ratio is 1: 1,1 : 2 and 2: 1.
Further, in step (3), 600 DEG C -650 DEG C of phosphatization temperature, phosphorus China's time 0.5-1.5h.
A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials, includes the following steps:A kind of CoP3And Ni2P two The preparation method of phase composite materials, which is characterized in that include the following steps:0.03492g Co(NO3)2·6H2O 0.02852g NiCl2·6H2OWith 0.072g urea, it is dissolved in deionized water In (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves and in an oven It is heated to 150 DEG C 2-5 hours, is subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in the upstream side of tube furnace, The above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat, by sample in 600 DEG C of -650 DEG C of heating and thermal insulations 0.5h-1.5h, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
A kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:0.02328g Co(NO3)2·6H2O0.03803g NiCl2·6H2OWith 0.072g urea, it is dissolved in In deionized water (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves simultaneously It is heated to 150 DEG C in an oven 2-5 hours, is subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in tube furnace The above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat by upstream side, by sample in 600 DEG C of -650 DEG C of heating 0.5h-1.5h is kept the temperature, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
A kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:0.04656g Co(NO3)2·6H2O0.01901g NiCl2·6H2OWith 0.072g urea, it is dissolved in In deionized water (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves simultaneously It is heated to 150 DEG C in an oven 2-5 hours, is subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in tube furnace The above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat by upstream side, by sample in 600 DEG C of -650 DEG C of heating 0.5h-1.5h is kept the temperature, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
CoP prepared by the present invention3And Ni2P two-phase composite materials can complete phosphatization in low temperature shorter time, and existing Rich phosphorous transition metal phosphide is compared, it is an advantage of the invention that in lower temperature (600-650 DEG C) and short period (0.5- Phosphatization is completed in 1.5h), and that obtain is three-dimensional flower-shaped CoP3And Ni2P two-phase composite materials.This CoP3And Ni2P two-phases Composite material has superior electrolysis water H2-producing capacity.When this material is with 0.3mg/cm2When being attached in rotating disk electrode (r.d.e), When overpotential is 135mV, current density can reach 30mA/cm2
Description of the drawings
Fig. 1 is the scanning electron microscope diagram piece of CoNi double-metal hydroxides.
Fig. 2 is CoP3And Ni2The scanning electron microscope diagram piece of P two-phase composite materials.
Fig. 3 is three electrode test CoP3And Ni2The linear sweep voltammetry of P two-phase composite material electro-catalysis H2-producing capacities is bent Line.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair Bright part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, ordinary skill Personnel's all other embodiments obtained under the premise of without creative work, shall fall within the protection scope of the present invention.
A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials, which is characterized in that with CoNi bimetal hydroxides Object is presoma, and three-dimensional flower-shaped CoP is obtained by the interior phosphatization of low-temperature short-time3And Ni2P two-phase composite nano materials.
Proposed by the present invention is CoP3And Ni2The preparation method of P two-phase composite nano materials, includes the following steps:
1. a certain amount of Co (NO3)2·6H2O, NiCl2·6H2Hydrothermal synthesis is spent under certain temperature in O and urea reaction kettle Shape CoNi duplex metal hydroxide nanometer pieces.Preferably, best preparation method is:Co(NO3)2·6H2O, NiCl2·6H2O Addition molecular weight ratio for 1: 1, temperature is 150 DEG C, time 3h.
2. the sample that step 1 is obtained is placed in tube furnace with a certain amount of sodium hypophosphite and carries out phosphatization, it is preferred that it is most Good preparation method is:650 DEG C of phosphatization temperature, phosphorus China's time 1h.
4. samples with water and ethyl alcohol after phosphatization is taken to rinse repeatedly several times, then dry.
Compared with existing rich phosphorous transition metal phosphide, it is an advantage of the invention that in lower temperature (600-650 DEG C) and Phosphatization is completed in short period (0.5-1.5h), and that obtain is three-dimensional flower-shaped CoP3/Ni2P nano hybrids.This CoP3/ Ni2P nano hybrids material has superior electrolysis water H2-producing capacity.When this material is with 0.3mg/cm2It is attached to rotational circle When on disc electrode, when overpotential is 135mV, current density can reach 30mA/cm2
Specific embodiment:
Embodiment one synthesizes flower-shaped CoNi double-metal hydroxides:0.02328g Co are synthesized by one step hydro thermal method (NO3)2·6H 2O0.03803gNiCl6H2O and 0.072g urea (0.012g), It is dissolved in deionized water (80mL).After being ultrasonically treated at least 30 minutes, 100mL stainless steel high pressures are then transferred the solution into It is heated in kettle and in an oven 150 DEG C 2 hours.It is subsequently cooled to room temperature.Product is collected, is washed with water and in certain temperature It is 10 hours or more dry in baking oven.
Sodium hypophosphite (1.0g) is placed in the upstream side of tube furnace, flower-shaped CoNi double-metal hydroxides (100mg) are put Downstream in another porcelain boat, by sample in 650 DEG C of heating and thermal insulation 0.5h, heating speed is 3 DEG C/min.Then in Ar2It protects The lower cooled to room temperature of shield.
Embodiment two:The hydro-thermal time is changed to 3h, other processing are the same as implementation example one.
Embodiment three:The hydro-thermal time is changed to 4h, other processing are the same as implementation example one.
Example IV:The hydro-thermal time is changed to 5h, other processing are the same as implementation example one.
Embodiment five:0.03492g Co (NO will be changed in hydrothermal synthesis3)2·6H2O0.02852g Other processing are the same as implementation example two.
Embodiment six:0.04656g Co (NO will be changed in hydrothermal synthesis3)2·6H2O0.01901g Other processing are the same as implementation example two.
Embodiment seven:Phosphating time is changed to 1h, other processing are the same as implementation example five.
Embodiment eight:Phosphating time is changed to 1.5h, other processing are the same as implementation example five.
It should be understood that although with reference to its illustrative embodiment, particularly shown and description is carried out to the present invention, It should be understood by those skilled in the art that without departing substantially from the spirit and model by the present invention as defined in the claims Under conditions of enclosing, the variation of various forms and details can be carried out wherein, can carry out the arbitrary combination of various embodiments.

Claims (7)

1. a kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that using CoNi double-metal hydroxides before Body is driven, three-dimensional flower-shaped CoP is obtained by the interior phosphatization of low-temperature short-time3And Ni2P two-phase composite nano materials.
2. a kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:
(1) a certain amount of Co (NO3)2·6H2O, NiCl2·6H2Hydrothermal synthesis is flower-shaped under certain temperature in O and urea reaction kettle CoNi duplex metal hydroxide nanometer pieces.
(2) sample for obtaining step (1) is placed in tube furnace with a certain amount of sodium hypophosphite and carries out phosphatization;
(3) samples with water and ethyl alcohol after phosphatization is taken to rinse repeatedly several times, is then dried.
3. a kind of CoP according to claim 23And Ni2The preparation method of tri- two-phase composite materials of P, it is characterised in that:Step Suddenly Co (NO in (1)3)2·6H2O, NiCl2·6H2The adding proportion of O is molecular weight than 1: 1,1: 2 and 2: 1.
4. a kind of CoP according to claim 23And Ni2The preparation method of P two-phase composite materials, it is characterised in that:Step (2) in, 600 DEG C -650 DEG C of phosphatization temperature, phosphorus China's time 0.5-1.5h.
5. a kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:0.03492gCo (NO3)2·6H2O0.02852g NiCl2·6H2OWith 0.072g urea, it is dissolved in In ionized water (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves and 150 DEG C are heated in baking oven 2-5 hours, are subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in the upper of tube furnace Side is swum, the above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat, sample is protected in 600 DEG C of -650 DEG C of heating Warm 0.5h-1.5h, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
6. a kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:0.02328gCo (NO3)2·6H2O0.03803g NiCl2·6H2OWith 0.072g urea, it is dissolved in In ionized water (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves and 150 DEG C are heated in baking oven 2-5 hours, are subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in the upper of tube furnace Side is swum, the above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat, sample is protected in 600 DEG C of -650 DEG C of heating Warm 0.5h-1.5h, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
7. a kind of CoP3And Ni2The preparation method of P two-phase composite materials, which is characterized in that include the following steps:0.04656gCo (NO3)2·6H2O0.01901g NiCl2·6H2OWith 0.072g urea, it is dissolved in In ionized water (80mL).After being ultrasonically treated at least 30 minutes, then transfer the solution into 100mL stainless steel autoclaves and 150 DEG C are heated in baking oven 2-5 hours, are subsequently cooled to room temperature, collect product.1.0g sodium hypophosphites are placed in the upper of tube furnace Side is swum, the above-mentioned compound precursors of 100mg are placed in the downstream in another porcelain boat, sample is protected in 600 DEG C of -650 DEG C of heating Warm 0.5h-1.5h, heating speed is 3 DEG C/min, then in Ar2The lower cooled to room temperature of protection.
CN201810044276.8A 2018-01-10 2018-01-10 A kind of CoP3And Ni2The preparation method of P two-phase composite nano materials Pending CN108264029A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112403505A (en) * 2020-12-09 2021-02-26 大唐南京环保科技有限责任公司 CoP-g-C3N4Electronic current collector photocatalyst and preparation method and application thereof
CN112614994A (en) * 2020-12-10 2021-04-06 三峡大学 Preparation method of water system zinc-cobalt battery laminated positive electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105903482A (en) * 2016-05-20 2016-08-31 宁夏大学 CoP/TiO2 composite photocatalyst as well as preparation and use thereof
CN107416785A (en) * 2017-07-20 2017-12-01 中北大学 Flower-shaped CoP3/Ni2The preparation method and application of P nano hybrids
CN107486198A (en) * 2017-08-02 2017-12-19 江苏大学 A kind of Bi based on the modification of peach blossom biomass carbon2WO6The Preparation method and use of composite photo-catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105903482A (en) * 2016-05-20 2016-08-31 宁夏大学 CoP/TiO2 composite photocatalyst as well as preparation and use thereof
CN107416785A (en) * 2017-07-20 2017-12-01 中北大学 Flower-shaped CoP3/Ni2The preparation method and application of P nano hybrids
CN107486198A (en) * 2017-08-02 2017-12-19 江苏大学 A kind of Bi based on the modification of peach blossom biomass carbon2WO6The Preparation method and use of composite photo-catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112403505A (en) * 2020-12-09 2021-02-26 大唐南京环保科技有限责任公司 CoP-g-C3N4Electronic current collector photocatalyst and preparation method and application thereof
CN112403505B (en) * 2020-12-09 2023-09-01 大唐南京环保科技有限责任公司 CoP-g-C 3 N 4 Electric subset fluid photocatalyst, preparation method and application thereof
CN112614994A (en) * 2020-12-10 2021-04-06 三峡大学 Preparation method of water system zinc-cobalt battery laminated positive electrode material

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