CN102614880A - Preparation and application of carbon-supported amorphous metallic nickel - Google Patents

Preparation and application of carbon-supported amorphous metallic nickel Download PDF

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CN102614880A
CN102614880A CN2012100085918A CN201210008591A CN102614880A CN 102614880 A CN102614880 A CN 102614880A CN 2012100085918 A CN2012100085918 A CN 2012100085918A CN 201210008591 A CN201210008591 A CN 201210008591A CN 102614880 A CN102614880 A CN 102614880A
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carbon
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noble metal
amorphous metal
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王辉
王星砾
王荣方
王克亮
答花花
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Northwest Normal University
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    • Y02E60/50—Fuel cells

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Abstract

The invention provides a preparation method for carbon-supported amorphous metallic nickel, which belongs to the technical field of metallic materials. The carbon-supported amorphous metallic nickel provided in the invention is prepared by using NiCl2.6H2O and ethylene diamine tetraacetic acid as raw materials and employing a hydrothermal process for reduction; amorphous metallic nickel has good dispersibility and a small specific surface area on a carbon support; a fuel cell noble metal catalyst using amorphous metallic nickel as a precursor has the characteristics of good stability, high activity, a long service life and the like, shows good catalytic activity during the process of catalytic oxidation of the anode of a fuel cell and is a high performance catalyst for a fuel cell. Since amorphous metallic nickel can produce electronic effects and synergism together with noble metal atoms (e.g., platinum atoms, palladium atoms, platinum-ruthenium atoms and the like), the catalysis effect of the catalyst is promoted, resistance to CO poisoning of the catalyst is enhanced, the usage amount of noble metals is effectively reduced, and cost for the catalyst is reduced.

Description

A kind of carbon carries the preparation and the application of amorphous metal nickel
Technical field
The invention belongs to the metal material technical field, relate to a kind of carbon and carry amorphous metal nickel material and preparation method thereof; The invention still further relates to this carbon and carry amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts.
Background technology
Metal Ni is a kind of transition metal with magnetic, and matter is hard, and resistance to corrosion is strong, hear resistance, plasticity and good toughness.Metal Ni is not only the basic material of making nickel alloy, also can form alloy with metallic elements such as Fe, Cu, Al.At present, Ni and alloy thereof can be used for multiple technologies such as rocketry equipment, atomic pile, alkaline storage battery, porous filter, catalyst and corrosion protection plating.
Amorphous metal is claimed again " glassy metal ", is meant a kind of metal material of structural disorder on atomic scale, and its design feature is: shortrange order, and shortrange order district surface coordination atom height is unsaturated, the surface can be higher; Long-range is unordered, and along with the increase that atom is given an example, interatomic correlation weakens rapidly; When surpassing some atomic distances; Correlation approaches complete disordered state, and atom presents topology at three dimensions and need not to arrange, and is a kind of material that does not have three dimensions atom periodic arrangement.Because the unique texture of amorphous metal makes it have physical and chemical performances such as unique mechanical performance, magnetic performance, electric property, hydrogen storage property, catalytic performance.
Metal Ni not only can form amorphous metal alloy with other element, and amorphous metal Ni can be used as the precursor metal of fuel cell noble metal core-shell structure catalyst.At present, noble metal catalyst like Pt/C etc., is the commercial catalysts of comparative maturity, in fuel cell catalysis plurality of applications is arranged.But the intermediate product that traditional P t/C catalyst adsorbs oxidation of alcohols easily causes catalyst poisoning to lose efficacy, and Pt costs an arm and a leg, resource-constrained, to a great extent limit the commercialized development of fuel cell.With the precursor of amorphous metal Ni as the Pt catalyst, make the catalyst of nucleocapsid structure, not only, can promote the catalytic effect of catalyst, and can significantly reduce the consumption of precious metals pt owing to electronic effect and synergy between Pt atom and the Ni atom.
Summary of the invention
The objective of the invention is in order to provide a kind of carbon to carry the preparation method of amorphous metal nickel.
Another object of the present invention provides a kind of this carbon and carries amorphous metal nickel as precursor, the application in the preparation fuel cell noble metal catalysts.
One, carbon carries the preparation of amorphous metal nickel
Carbon of the present invention carries the preparation method of amorphous metal nickel, is at N 2Under the condition, (volume ratio of second alcohol and water is 1:1 ~ 1:2), with NiCl in the mixed solvent of second alcohol and water 26H 2O and ethylenediamine tetra-acetic acid mix with the mass ratio of 1:2 ~ 1:5, regulation system pH=12 ~ 14; In system, add NiCl 26H 2The carbon dust that the O quality is 1 ~ 1.5 times stirs and ultrasonic dispersion; Add NiCl again 26H 2The reducing agent hydrazine hydrate that the O quality is 1 ~ 2 times, in 90 ~ 160 ℃ of reaction 4 ~ 6h, after the cooling, with the black pulpous state solution suction filtration of gained, vacuum drying obtains the amorphous metal nickel that carbon carries fast.
Here, the selection of part directly has influence on the crystal formation of metal Ni, does part with ethylenediamine tetra-acetic acid (EDTA) and can obtain carbon and carry amorphous metal Ni.If use natrium citricum as part, next that obtain is crystallinity preferred metal Ni in identical condition.
Carbon through many present invention such as XRD, BET, EDX preparation structure, the performance of carrying amorphous metal nickel analyzed explanation below.
Fig. 1 carries X-ray diffraction (XRD) collection of illustrative plates of amorphous metal nickel for the carbon of the present invention's preparation.Fig. 2 carries X-ray diffraction (XRD) collection of illustrative plates of crystalline state metal Ni for the carbon of doing part with natrium citricum with this method.Comparison diagram 1,2, carbon carry (111) that crystalline state metal Ni does not appear in amorphous nickel, and (200), the characteristic crystal face diffraction maximum of (220) and (311) is just 2 θ=44 ° of (111) crystal face diffraction maximums of having located to occur Ni, the main existence that has proved metal Ni is an amorphous state.
Fig. 3 carries the BET specific area resolution chart of amorphous metal Ni for the carbon of the present invention's preparation.The specific area that records amorphous metal Ni/C is 126.451 m2/g.
Fig. 4 is the EDX figure of the amorphous metal Ni of the present invention's preparation.The result displayed explanation of Fig. 4 mainly contains Ni, the existence of C element in amorphous state Ni/C sample.
The carbon of the present invention preparation carries amorphous metal nickel/C, the quality of metal Ni be carbon carry amorphous metal nickel/C quality 20% ~ 25%.
In sum, the present invention adopts hydro-thermal method, through regulating the crystal formation of part with control metal Ni; Make carbon and carried amorphous metal Ni/C; Wherein, nickle atom is shortrange order, long-range lack of alignment, and its surface has the higher unsaturated center of concentration; Therefore, can be used as the catalyst that precursor is used to prepare the fuel cell noble metal.
Two, the preparation of NiPt/C eelctro-catalyst
Carrying amorphous metal nickel with above-mentioned carbon as the method for precursor preparation fuel cell noble metal catalysts is: the salt or the acid of noble metal are dissolved in the ethylene glycol, stir; Regulate pH=8 ~ 10 with the ethylene glycol solution of KOH, the carbon that adds 0.5 ~ 5 times of precious metal salt or sour quality carries amorphous metal nickel, stirs, ultrasonic 0.1 ~ 0.5 hour, then in 160 ~ 180 ℃ of back flow reaction 4 ~ 10 h; Suction filtration, washing, drying obtains fuel cell noble metal catalysts.
The salt of said noble metal is palladium bichloride, ruthenic chloride; The acid of said noble metal is chloroplatinic acid.
In the ethylene glycol solution of said KOH, the mass percent of KOH is 5 ~ 10%.
In the noble metal catalyst of above-mentioned preparation, the noble metal mass fraction is 10% ~ 30%.
Fig. 5 is for carrying transmission electron microscope (TEM) figure that amorphous metal nickel is the NiPt/C catalyst of precursor preparation with carbon of the present invention.As can be seen from Figure 5, the NiPt/C catalyst is microballoon, distribution uniform on carbon carrier.
The performance test of NiPt/C catalyst: at 0.5 M H 2SO 4Carried out the cyclic voltammetric test in the solution, and compared with 20 %wt Pt/C catalyst.Fig. 6 is that 20 %wt Pt/C and NiPt/C are at 0.5 M H 2SO 4Cyclic voltammetric resolution chart in the solution.The result of Fig. 6 shows: the NiPt/C catalyst characteristic oxidation/reduction peak of Pt occurred at-0.2 V ~ 0 V place, has explained that this catalyst surface is by the former subcovering of metal Pt.
The NiPt/C catalyst is tested the catalytic effect of methyl alcohol: at 0.5 M CH 3CH 2OH/H 2SO 4Carry out the cyclic voltammetric test in the solution, and compare with 20%wt Pt/C catalyst.Fig. 7 is that 20%wt Pt/C and NiPt/C are at 0.5 M CH 3CH 2OH/H 2SO 4Cyclic voltammetric resolution chart in the solution.Can find out that by Fig. 7 the oxidation peak current of NiPt/C catalyst ethanol is 0.32 A/mgPt, and 20 %wt Pt/C catalyst are 0.21 A/mgPt, therefore, under identical Pt carrying capacity, prepare catalyst with the present invention and have higher oxidation peak current.
In sum; Carbon with the present invention's preparation carries amorphous metal nickel as precursor metal; The NiPt/C catalyst of preparation has characteristics such as good stability, active height, long service life; In Ethanol Oxidation, demonstrating good catalytic activity, is the high performance catalyst that is used for alcohol fuel cell.Because carrying amorphous metal nickel, carbon can produce electronic effect and synergy with precious metal atom (like pt atom, palladium atom, platinum ruthenium atom etc.); Not only promoted the catalytic effect of catalyst; And strengthened the anti-CO poisoning capability of catalyst; And effectively reduced the consumption of noble metal, reduced the catalyst cost.
Description of drawings
Fig. 1 carries X-ray diffraction (XRD) collection of illustrative plates of amorphous state Ni/C for the carbon of the present invention's preparation.
Fig. 2 is for make X-ray diffraction (XRD) collection of illustrative plates of the crystalline state metal Ni of part preparation under the same conditions with natrium citricum.
Fig. 3 is the BET specific area resolution chart of the amorphous metal Ni of the present invention's preparation.
Fig. 4 is the EDX figure of the amorphous metal Ni of the present invention's preparation.
Fig. 5 is with transmission electron microscope (TEM) figure of amorphous state Ni/C as the NiPt/C catalyst of precursor preparation.
Fig. 6 is that 20 %wt Pt/C and NiPt/C catalyst are at 0.5 M H 2SO 4Cyclic voltammetric resolution chart in the solution.
Fig. 7 is that 20%wt Pt/C and NiPt/C catalyst are at 0.5 M CH 3CH 2OH/H 2SO 4Cyclic voltammetric resolution chart in the solution.
The specific embodiment
Through specific embodiment amorphous metallic material of the present invention and composite NiPt/C Preparation of catalysts thereof are further specified below.
Embodiment 1
(1) carries the preparation of carbon amorphous metal Ni/C
In 100 ml round-bottomed flasks, add 25 ml ethanol and three water of 25 ml, feed N 2After two hours, add 0.8 g ethylenediamine tetra-acetic acid (EDTA), stir, ultrasonicly make its dissolving, add 0.3 g NiCl again 26H 2O stirs the back and adds 2 g KOH conditioned reaction liquid to pH=14, in round-bottomed flask, adds 15ml hydrazine hydrate (80%) and 0.3g carbon carrier (Vulcan XC-72R) again, and stirring is also ultrasonic, and this process is all at logical N 2Condition under carry out.With the reactant liquor agitated reactor of packing into,, obtain the pulpous state solution of the amorphous metal Ni/C of black afterwards in 120 ℃ of reaction 4h.Suction filtration, cooling fast in cold water, 50 ~ 60 ℃ of vacuum drying obtain carbon and carry amorphous metal Ni.
Carbon carries among amorphous metal nickel/C, and the quality of metal Ni is 20 % that carbon carries amorphous metal nickel/C quality.
(2) NiPt/C Preparation of catalysts
The chloroplatinic acid H that in flask, adds 30 ml ethylene glycol (EG) and 2.91ml (20 mg/ml) successively 2PtCl 6, regulating pH=8 with 5% usefulness KOH/EG solution, the 100 mg Ni/C that adding step (1) makes stir and at 180 ℃ of reaction 9h, filter, washing, drying gets the NiPt/C catalyst.Metal Pt accounts for 18% of precursor Ni/C quality in the catalyst.
Detect with cyclic voltammetry: the current density of this catalyst n iPt/C catalysis ethanol is 0.32 A/mgPt, and commercial Pt/C catalyst improves 43% (under the similarity condition, the current density of Pt/C catalyst is 0.21 A/mgPt).
Embodiment 2
(1) preparation of amorphous metal Ni/C
In 100 ml round-bottomed flasks, add 25 ml ethanol and three water of 25 ml, feed N 2After two hours, add 0.8 g ethylenediamine tetra-acetic acid (EDTA), stir, ultrasonicly make its dissolving, add 0.3 g NiCl again 26H 2O stirs the back and adds 3 g KOH conditioned reaction liquid to pH=13, in round-bottomed flask, adds 15 ml hydrazine hydrates (80%) and 0.3g carbon carrier (Vulcan XC-72R) again, and stirring is also ultrasonic, and this process is all at logical N 2Condition under carry out.With the reactant liquor agitated reactor of packing into,, obtain the pulpous state solution of the amorphous metal Ni/C of black afterwards in 90 ℃ of reaction 5h.Suction filtration, cooling fast in cold water, 50 ~ 60 ℃ of vacuum drying obtain carbon and carry amorphous metal Ni.
(2) NiPd/C Preparation of catalysts
In flask, add 30 mg PdCl 2With a small amount of concentrated hydrochloric acid, ultrasonicly make its dissolving, add 30 ml EG afterwards, regulate pH=10 with 5% usefulness KOH/ ethylene glycol solution; Add the 100 mg Ni/C precursors make, stir, ultrasonic 0.5 hour, at 160 ℃ of reaction 8h, filter afterwards; Washing, drying gets the NiPt/C catalyst.Metal Pd accounts for 20% of precursor Ni/C quality.
Detect with cyclic voltammetry: the current density of this catalyst n iPd/C catalysis formic acid is 0.38 A/mgPt, and commercial Pt/C catalyst improves 31% (under the similarity condition, the current density of Pd/C catalyst is 0.29 A/mgPt).
Embodiment 3
(1) preparation of amorphous metal Ni/C
In 100 ml round-bottomed flasks, add 25 ml ethanol and three water of 25 ml, feed N 2After two hours, add 0.8 g ethylenediamine tetra-acetic acid (EDTA), stir, ultrasonicly make its dissolving, add 0.3 g NiCl again 26H 2O stirs the back and adds 2 g KOH conditioned reaction liquid to pH=12, in round-bottomed flask, adds 15 ml hydrazine hydrates (80%) and 0.45g carbon carrier (Vulcan XC-72R) again, and stirring is also ultrasonic, and this process is all at logical N 2Condition under carry out.With the reactant liquor agitated reactor of packing into,, obtain the pulpous state solution of the amorphous metal Ni/C of black afterwards in 160 ℃ of reaction 4h.Suction filtration, cooling fast in cold water, 50 ~ 60 ℃ of vacuum drying obtain carbon and carry amorphous metal Ni.
(2) NiPtRu/C Preparation of catalysts
In flask, add 30 ml EG, 5.6 ml, 20 mg/ml H successively 2PtCl 6With 2.9mL 20 mg/ml RuCl 3XH 2O stirs and to make its dissolving, regulates pH=10 with 5% usefulness KOH/EG solution, adds the 150 mg Ni/C precursors that make, and stirs, ultrasonic 0.5 hour, at 160 ℃ of reaction 8h, filters afterwards, washs, and drying gets the NiPtRu/C catalyst.
The amount of metal of PtRu accounts for 30% of Ni/C precursor quality, wherein Pt:Ru (atomic ratio)=1:1.
Detect with cyclic voltammetry: the current density of this catalyst n iPtRu catalysis methanol is 0.35 A/mgPt, and commercial Pt/C catalyst improves 35% (under the similarity condition, the current density of Pt/C catalyst is 0.26 A/mgPt).

Claims (8)

1. a carbon carries the preparation method of amorphous metal nickel, is at N 2Under the condition, in the mixed solvent of second alcohol and water, with NiCl 26H 2O and ethylenediamine tetra-acetic acid mix with the mass ratio of 1:2 ~ 1:5, regulation system pH=12 ~ 14; In system, add NiCl 26H 2The carbon dust that the O quality is 1 ~ 1.5 times stirs and ultrasonic dispersion; Add NiCl again 26H 2The reducing agent hydrazine hydrate that the O quality is 1 ~ 2 times, in 90 ~ 160 ℃ of reaction 4 ~ 6h, after the cooling, with the black pulpous state solution suction filtration of gained, vacuum drying obtains the amorphous metal nickel that carbon carries fast.
2. carbon carries the preparation method of amorphous metal Ni according to claim 1, and it is characterized in that: the mixed solvent of said second alcohol and water, the volume ratio of ethanol and water are 1:1 ~ 1:2.
3. carbon carries the preparation method of amorphous metal Ni according to claim 1, and it is characterized in that: said vacuum drying is under 50 ~ 60 ℃, to carry out.
4. the carbon of method preparation carries amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts according to claim 1.
5. carry amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts like the said carbon of claim 4, it is characterized in that: the salt or the acid of noble metal are dissolved in the ethylene glycol, stir; Ethylene glycol solution with KOH is regulated pH=8 ~ 10; The carbon that adds 0.5 ~ 5 times of salt or the sour quality of noble metal carries amorphous metal nickel, stirs, ultrasonic 0.1 ~ 0.5 hour, then in 160 ~ 180 ℃ of back flow reaction 4 ~ 10 h; Suction filtration, washing, drying obtains fuel cell noble metal catalysts.
6. carry amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts like the said carbon of claim 5, it is characterized in that: the salt of said noble metal is palladium bichloride, ruthenic chloride.
7. carry amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts like the said carbon of claim 5, it is characterized in that: the acid of said noble metal is chloroplatinic acid.
8. carry amorphous metal nickel as the application of precursor in the preparation fuel cell noble metal catalysts like the said carbon of claim 5, it is characterized in that: in the ethylene glycol solution of said KOH, the mass percent of KOH is 5 ~ 10%.
CN2012100085918A 2012-01-12 2012-01-12 Preparation and application of carbon-supported amorphous metallic nickel Pending CN102614880A (en)

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Cited By (7)

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CN104485463A (en) * 2014-12-30 2015-04-01 西北师范大学 Alloy-oxide composite carbon material noble-metal-loaded catalyst and preparation method of catalyst
CN106423242A (en) * 2016-09-12 2017-02-22 天津工业大学 Preparation method of nitrogen-doped nickel/carbon high-performance ethanol oxidation catalyst
CN106582656A (en) * 2016-12-08 2017-04-26 浙江优创材料科技股份有限公司 Synthesis method for nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile
CN109107596A (en) * 2018-08-20 2019-01-01 河南师范大学 The preparation method of the carbon nano enzyme of active metal and nitrogen codope and its application that hydrogen peroxide is detected as nanometer bio probe
CN109950554A (en) * 2019-01-09 2019-06-28 柯良节 A kind of graphene-supported metal nano island catalyst and the preparation method and application thereof
CN113492012A (en) * 2020-04-03 2021-10-12 中国石油化工股份有限公司 Non-noble metal Ni-based catalyst and preparation method thereof, and method for preparing cyclopentane by cyclopentadiene hydrogenation
CN114538433A (en) * 2022-02-25 2022-05-27 中南大学 Method for preparing quick-charging graphite with single-metal-doped defects

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Publication number Priority date Publication date Assignee Title
CN104485463A (en) * 2014-12-30 2015-04-01 西北师范大学 Alloy-oxide composite carbon material noble-metal-loaded catalyst and preparation method of catalyst
CN104485463B (en) * 2014-12-30 2017-01-04 西北师范大学 A kind of alloy-oxide complex carbon material supported precious metal catalyst and preparation method thereof
CN106423242A (en) * 2016-09-12 2017-02-22 天津工业大学 Preparation method of nitrogen-doped nickel/carbon high-performance ethanol oxidation catalyst
CN106582656A (en) * 2016-12-08 2017-04-26 浙江优创材料科技股份有限公司 Synthesis method for nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile
CN109107596A (en) * 2018-08-20 2019-01-01 河南师范大学 The preparation method of the carbon nano enzyme of active metal and nitrogen codope and its application that hydrogen peroxide is detected as nanometer bio probe
CN109950554A (en) * 2019-01-09 2019-06-28 柯良节 A kind of graphene-supported metal nano island catalyst and the preparation method and application thereof
CN113492012A (en) * 2020-04-03 2021-10-12 中国石油化工股份有限公司 Non-noble metal Ni-based catalyst and preparation method thereof, and method for preparing cyclopentane by cyclopentadiene hydrogenation
CN113492012B (en) * 2020-04-03 2024-06-11 中国石油化工股份有限公司 Non-noble metal Ni-based catalyst, preparation method thereof and method for preparing cyclopentane by cyclopentadiene hydrogenation
CN114538433A (en) * 2022-02-25 2022-05-27 中南大学 Method for preparing quick-charging graphite with single-metal-doped defects
CN114538433B (en) * 2022-02-25 2023-11-10 中南大学 Method for preparing quick graphite filling with single metal doping defect

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Application publication date: 20120801