CN109023416A - The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel - Google Patents
The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel Download PDFInfo
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Abstract
The invention belongs to field of material synthesis technology, and in particular to the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel and its research of Hydrogen Evolution Performance.The present invention combines polysaccharide and graphene, it acts on forming hydrogel using the chelating of polysaccharide and metal ion Co and Ni, then freeze-drying forms aeroge, and further phosphatization forms NiCoP@graphene aerogel composite material, for efficient liberation of hydrogen under acid condition.The advantage of the invention is that environmentally protective, at low cost, preparation process is easy, and catalyst obtained is easy to large-scale industrial production and has excellent electro catalytic activity and good liberation of hydrogen stability.
Description
Technical field
The invention belongs to field of material synthesis technology, and in particular to NiCoP@graphene aerogel efficient liberation of hydrogen composite wood
The preparation method of material and its research of Hydrogen Evolution Performance.
Background technique
Currently, facing mankind the energy crisis that gets worse and problem of environmental pollution, seeking novel environment friendly cleaning can replace
Become for the energy and solves current crisis significant challenge.Hydrogen Energy because have many advantages, such as calorific value it is high, it is pollution-free and using it is various informative at
For one of the main representative of novel environment friendly clean energy resource, it is known as being a kind of ideal alternative fossil fuel by scientific circles
New energy has unrivaled huge advantage and unlimited wide application prospect.However how to be obtained by effective approach
Relatively inexpensive hydrogen energy source is the main contents of current researcher research.China's water resource very abundant, water electrolysis hydrogen production
Be obtain hydrogen energy source effective way, but water be electrolysed efficient energy conversion it is low be restrict its industrialized production factor it
One, therefore design and develop high-performance, inexpensive electrocatalytic hydrogen evolution (HER) catalyst is extremely important.
In recent years, the application of transient metal sulfide, nitride, carbide and phosphide in HER greatly attracts
The concern of researcher.Applied to the elctro-catalyst in HER, either transient metal sulfide and nitride or carbide
And phosphide, they have a common feature: all there is transition metal element, the sky that transition metal provides in metallic compound
D- track and unpaired electronics can combine Hydrogen Proton.The nonmetallic P atom of electronegativity and orphan in transition metal phosphide
Vertical metallic atom is respectively served as proton acceptor site and hydride acceptor site, can theoretically show superior HER
Activity.Experiment and research also has shown that double-metal phosphide NiCoP has electro-chemical activity in acidic electrolysis bath, still,
NiCoP is there is also being easy to reunite, and low activity is easy to the disadvantages of inactivating, the application that this severely limits them in HER.
The new material for the three-dimensional net structure that natural polysaccharide base aeroge is constituted as nanoparticle, because it has typical case
The spies such as porous network structure, high-specific surface area, high porosity, low-density, lower thermal conductivity, low-k, high absorption property
Point, and because of dimensional effect, skin effect and the macro quanta tunnel effect caused by the nanoscale of its skeleton and hole,
The various fields such as mechanics, calorifics, optics have a wide range of applications.Sodium alginate is as one of natural polysaccharide, since its is good
Good biological degradability and biocompatibility, is widely used in the fields such as pharmacy, chemical industry, biology, food.Sodium alginate soln with
Metal cation chelating, the aeroge of formation are being curbed environmental pollution, by wide coverage in terms of degradation of organic substances, but in electrification
It is rarely reported in terms of learning liberation of hydrogen.
Summary of the invention
The present invention is intended to provide the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel, this method pass through
Hydrogel is made in simple sol-gal process, then obtains the efficient liberation of hydrogen of NiCoP@graphene aerogel by the method for high temperature phosphorization
Composite material.The efficient liberation of hydrogen composite material of NiCoP@graphene aerogel prepared by the present invention has excellent electrocatalytic hydrogen evolution
Energy.
The present invention is more novel to be acted on by the chelating of sodium alginate soln and metal Co, Ni, due to being related to two kinds of gold
Belong to ion, needs to adjust Co (NO3)2·6H2O、Ni(NO3)2·6H2O, the additional amount of sodium alginate and GO powder, digestion time
Equal technological parameters, form alginate hydrogel, and further high temperature phosphorization forms bimetallic NiCoP carbon airsetting after freeze-drying
The amount of specific graphene oxide is added by control, further improves its electronics conduction velocity, ultimately forms for glue (NiCoP@CA)
NiCoP@graphene aerogel (NiCoP@GA), greatly improves its electrochemical catalysis performance.
The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel, specifically includes the following steps:
(1) Co (NO is weighed3)2·6H2O and Ni (NO3)2·6H2O is dissolved into deionized water and stirs, and stirring forms Co
(NO3)2·6H2O and Ni (NO3)2·6H2O mixed solution A；
(2) it weighs sodium alginate (SA) and is poured into deionized water stirring and form uniform sodium alginate soln B；
(3) it weighs in GO powder injection sodium alginate soln B, ultrasound obtains dispersion liquid C in Ultrasound Instrument after stirring；
(4) solution C of certain volume is added dropwise in solution A at normal temperature dropwise, forms hydrogel；The hydrogel of formation
It is impregnated, is washed respectively with deionized water and ethyl alcohol after ageing；
(5) will ageing, impregnate, it is washed after hydrogel be freeze-dried in freeze drier until formation xerogel.
(6) xerogel and red phosphorus (P) are taken respectively, and red phosphorus is placed in tube furnace upstream position, and xerogel is placed in downstream, carries out high
Warm phosphatization finally obtains NiCoP@graphene aerogel.
In step (1), Co (NO3)2·6H2O、Ni(NO3)2·6H2O and the mass ratio of deionized water are 1:1:80.
In step (2), sodium alginate and Co (NO3)2·6H2The mass ratio of O is 4:5, the matter of sodium alginate and deionized water
Amount is than being 1:100.
In step (3), the mass ratio of GO and sodium alginate is 1:5；Ultrasonic time is 30min.
In step (4), the volume ratio of the solution A and solution C is 1:1；Digestion time is 8h；It is described with using deionized water
It impregnates, washing refers to: first being impregnated with deionized water, washing 3 times, each 2h of soaking time respectively with ethyl alcohol；It impregnated, washed with ethyl alcohol again
It washs 3 times, each 2h of soaking time.
In step (5), sublimation drying 48h.
In step (6), the mass ratio of the xerogel and red phosphorus is 1:1；The quality of red phosphorus is less than 1g, the quality of red phosphorus
Bigger, the easier appearance of high temperature is dangerous；Logical nitrogen is as protection gas, and calcination temperature is 800 DEG C, soaking time 4h, heating rate 4
℃/min。
The invention has the benefit that
(1) the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel prepared by the present invention, it is more novel by polysaccharide nickel
Cobalt-based aeroge is synthesized by high temperature phosphorization, and preparation process is simple, at low cost, is easy to large-scale industrial production, the material
With good electrochemical stability and Hydrogen Evolution Performance, before having good application in terms of solving environmental pollution and energy crisis
Scape.
(2) compared to the synthesis process of other synthesis double-metal phosphides, which passes through biomass alginic acid for the first time
Sodium is synthesized as presoma by a step high temperature phosphorization with Cobalt salts, nickel salt chelating, is compared and existing synthesis NiCoP composite wood
The technology of material is creative and novelty, while comparing simple NiCoP bulk catalyst, NiCoP@graphene aerogel
Efficient liberation of hydrogen composite material exhibits go out excellent chemical property.
(3) specific surface area high in electrochemical system and good electric conductivity play vital work to catalyst quality
With sodium alginate base aeroge has flourishing network hole configurations, and double-metal phosphide NiCoP is supported on graphene gas
On gel, the specific surface area of catalyst is greatly increased, flourishing network structure also functions to the fixation and dispersion of NiCoP
Good effect to increase effective contact area of catalyst and electrolyte increases the active site of catalyst, improves
Hydrogen Evolution Performance.The efficient liberation of hydrogen composite material of NiCoP@graphene aerogel, Tafel slope 63mV dec-1, current density is
10mA/cm2When overpotential be 109 mV；Have significantly with other document monomers NiCoP performance compared in terms of liberation of hydrogen
It improves.
(4) the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel can be used as the electrochemistry liberation of hydrogen catalysis of function admirable
Agent.Graphene aerogel (GA) structure has good hydrophily, can make the more graphene edges of electrolyte contacts and table
Face, the excellent conductivity of graphene greatly facilitate the transmission of charge, the stability of compound rear catalyst are effectively promoted.Cause
This, the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel improves catalyst to electrolysis water Hydrogen Evolution Performance, in electricity significantly
Catalysis practical application area has broad prospects.
Detailed description of the invention
Fig. 1 is the XRD spectrum of sample prepared by embodiment, is NiCoP bulk, NiCoP@carbon aerogels (NiCoP@
) and the XRD diagram of NiCoP@graphene aerogel (NiCoP@GA) CA；
Fig. 2 is that embodiment 1 (a) is the prepared NiCoP bulk Sample Scan electron microscope under 100nm multiplying power；(b) exist
The scanning electron microscope (SEM) photograph of NiCoP@GA sample under 100nm multiplying power；
Fig. 3 is that the efficient liberation of hydrogen composite material of NiCoP@GA prepared by embodiment 1 in an acidic solution imitate by electrochemistry liberation of hydrogen
Fruit figure；(a) it is the linear sweep voltammetry figure (LSV figure) of composite catalyst, (b) is the Tafel slope figure of composite catalyst
(Tafer figure).
Specific embodiment
To specific embodiment, the invention will be further described with reference to the accompanying drawings of the specification.
Embodiment 1:
Prepare NiCoP bulk material
(1) 0.5g Co (NO is weighed3)2·6H2O and 0.5g Ni (NO3)2·6H2O is dissolved into 40ml deionized water and stirs
It mixes, stirring forms Co (NO3)2·6H2O and Ni (NO3)2·6H2O mixed solution A.
(2) the NaOH solid for weighing 20mmol is dissolved in 10ml deionized water, and stirring 10min forms uniform solution B.
(3) solution B drop is instilled in solution A, stirs 10min, to fully reacting, be then centrifuged sediment, washing,
Dry, grinding forms grey powder.
(4) 0.4g grey powder and 0.5g red phosphorus (P) are taken respectively, and red phosphorus is placed in tube furnace upstream position, presoma grey
Powder is placed in downstream, lead to nitrogen as protection gas, calcination temperature be 800 DEG C, soaking time be 4 h, 4 DEG C/min of heating rate,
High temperature phosphorization is carried out, NiCoP bulk material is finally obtained.
Embodiment 2:
Prepare NiCoP@carbon aerogels (NiCoP@CA) efficiently liberation of hydrogen composite material
(1) 0.5g Co (NO is weighed3)2·6H2O and 0.5g Ni (NO3)2·6H2O is dissolved into 40ml deionized water and stirs
It mixes, stirring forms Co (NO3)2·6H2O and Ni (NO3)2·6H2O mixed solution A；
(2) sodium alginate (SA) for weighing 0.4g, which is poured into 40ml ionized water, to be vigorously stirred to form uniform sodium alginate
Solution B；
(3) the solution B drop of certain volume is injected into solution A at normal temperature, forms hydrogel.The hydrogel of formation
Ageing 8 hours, is then impregnated with deionized water, is washed 3 times, each 2h；Ethyl alcohol impregnates, and washs 3 times, each 2h.
(4) will ageing, impregnate, it is washed after hydrogel be freeze-dried in freeze drier 48 hours, until formation
Xerogel.
(5) xerogel and 0.5g red phosphorus (P), red phosphorus for taking 0.4g respectively are placed in tube furnace upstream position, and xerogel is placed in
Downstream leads to nitrogen as protection gas, and calcination temperature is 800 DEG C, soaking time 4h, 4 DEG C/min of heating rate, carries out high temperature phosphorous
Change, finally obtains NiCoP@carbon aerogels (NiCoP@CA).
Embodiment 3:
Prepare NiCoP@graphene carbon aeroge (NiCoP@GA) efficiently liberation of hydrogen composite material
(1) 0.5g Co (NO is weighed3)2·6H2O and 0.5g Ni (NO3)2·6H2O is dissolved into 40ml deionized water and stirs
It mixes, stirring forms Co (NO3)2·6H2O and Ni (NO3)2·6H2O mixed solution A；
(2) sodium alginate (SA) for weighing 0.4g, which is poured into 40ml ionized water, to be vigorously stirred to form uniform sodium alginate
Solution B；
(3) weigh 80mg GO powder injection solution B in, after stirring in Ultrasound Instrument ultrasound 30min, obtain dispersion liquid C；
(4) the solution C drop of 40ml is added dropwise in solution A at normal temperature, forms hydrogel.The hydrogel of formation is aged
It 8 hours, is then impregnated, is washed 3 times, each 2h with deionized water；Ethyl alcohol impregnates, and washs 3 times, each 2h.
(5) will ageing, impregnate, it is washed after hydrogel be freeze-dried in freeze drier 48 hours, until formation
Xerogel.
(6) xerogel and 0.5g red phosphorus (P), red phosphorus for taking 0.4g respectively are placed in tube furnace upstream position, and xerogel is placed in
Downstream leads to nitrogen as protection gas, and calcination temperature is 800 DEG C, soaking time 4h, 4 DEG C/min of heating rate, carries out high temperature phosphorous
Change, finally obtains NiCoP@graphene carbon aeroge (NiCoP@GA).
Fig. 1 is NiCoP bulk in Figure of description, the XRD diagram of NiCoP@CA and NiCoP@GA, from Fig. 1 it can be seen that
Diffraction maximum is respectively corresponded in 30.628,35.518,40.998,44.898,47.588,54.448,54.748 and 55.338
(110) of NiCoP standard card (JCPDS No.71-2336), (200), (111), (201), (210), (300), (002) and
(211) crystal face, to illustrate NiCoP bulk, NiCoP@CA and NiCoP@GA is successfully synthesized.
Fig. 2 (a) is scanning electron microscope (FESEM) figure of NiCoP bulk sample under 100nm multiplying power, from figure it can be seen that
There is no NiCoP bulk bulk reunion and particle diameter of the graphene aerogel as substrate larger；Fig. 2 (b) is NiCoP@GA sample
Scanning electron microscope (FESEM) figure of product under 100nm multiplying power, NiCoP nanoparticle is uniformly embedded in graphene aerogel in figure
Nanometer sheet in, graphene and carbon aerogels form three-dimensional transmission matrix together, can not only effectively organize NiCoP nanoparticle
Reunion, and can also greatly increase the specific surface area of catalyst, enhancing Hydrogen Proton transmission.
Fig. 3 (a) is NiCoP bulk, the linear voltammetric scan figure (LSV figure) of NiCoP@CA and NiCoP@GA, energy in figure
Enough find out that NiCoP bulk shows poor take-off potential and current density；The introducing of carbon aerogels, so that NiCoP@CA electricity
Chemical Hydrogen Evolution Performance has apparent improvement；When introducing graphene carbon aeroge, NiCoP@GA shows best electrochemistry
Hydrogen Evolution Performance, take-off potential 34mV, current density 10mA/cm2When overpotential be 109mV；It is several compound in Fig. 3 (b)
The Tafel slope figure of elctro-catalyst, wherein NiCoP GA shows most excellent Tafel slope 63mV/dec.
Claims (6)
- The preparation method of the efficient liberation of hydrogen composite material of 1.NiCoP@graphene aerogel, which is characterized in that molten by sodium alginate The effect of the chelating of liquid and metal Co, Ni, adjusts Co (NO3)2·6H2O、Ni(NO3)2·6H2O, sodium alginate and GO powder plus Enter amount, digestion time technological parameter forms alginate hydrogel, and further high temperature phosphorization forms bimetallic after freeze-drying The amount of specific graphene oxide is added by control, further improves its electronics conduction velocity, most end form for NiCoP carbon aerogels At NiCoP@graphene aerogel, its electrochemical catalysis performance is greatly improved, specific preparation process is as follows:(1) Co (NO is weighed3)2·6H2O and Ni (NO3)2·6H2O is dissolved into deionized water and stirs, and stirring forms Co (NO3)2· 6H2O and Ni (NO3)2·6H2O mixed solution A；(2) it weighs sodium alginate (SA) and is poured into deionized water stirring and form uniform sodium alginate soln B；(3) it weighs in GO powder injection sodium alginate soln B, ultrasound obtains dispersion liquid C in Ultrasound Instrument after stirring；(4) solution C of certain volume is added dropwise in solution A at normal temperature dropwise, forms hydrogel；The hydrogel of formation is aged It is impregnated, is washed respectively with deionized water and ethyl alcohol afterwards；(5) will ageing, impregnate, it is washed after hydrogel be freeze-dried in freeze drier until formation xerogel；(6) xerogel and red phosphorus are taken respectively, red phosphorus is placed in tube furnace upstream position, and xerogel is placed in downstream, high temperature phosphorization is carried out, Finally obtain NiCoP@graphene aerogel；In step (1), Co (NO3)2·6H2O、Ni(NO3)2·6H2O and the mass ratio of deionized water are 1:1:80；In step (2), sodium alginate and Co (NO3)2·6H2The mass ratio of O is 4:5, the mass ratio of sodium alginate and deionized water For 1:100；In step (3), the mass ratio of GO and sodium alginate is 1:5.
- 2. the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel as described in claim 1, feature exist In, in step (3), ultrasonic time 30min.
- 3. the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel as described in claim 1, feature exist In in step (4), the volume ratio of the solution A and solution C is 1:1；Digestion time is 8h；It is described to use deionized water and second Alcohol impregnates respectively, and washing refers to: first being impregnated with deionized water, washing 3 times, each 2h of soaking time；It is impregnated again with ethyl alcohol, washing 3 It is secondary, each 2h of soaking time.
- 4. the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel as described in claim 1, feature exist In, in step (5), sublimation drying 48h.
- 5. the preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel as described in claim 1, feature exist In in step (6), the mass ratio of the xerogel and red phosphorus is 1:1；The quality of red phosphorus is less than 1g, and the quality of red phosphorus is bigger, The easier appearance of high temperature is dangerous；For logical nitrogen as protection gas, calcination temperature is 800 DEG C, soaking time 4h, 4 DEG C of heating rate/ min。
- 6. the purposes of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel of method preparation as described in claim 1, is used for The electrochemistry liberation of hydrogen catalyst of liberation of hydrogen in acid condition.
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Cited By (5)
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| CN109778225A (en) * | 2019-01-31 | 2019-05-21 | 上海应用技术大学 | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation |
| CN110075885A (en) * | 2019-05-31 | 2019-08-02 | 中南林业科技大学 | Binary cobalt is Ni-based-carbon composite electrocatalyst and preparation method thereof |
| CN110323073A (en) * | 2019-06-28 | 2019-10-11 | 中国地质大学（北京） | A kind of oxygen doping phosphatization cobalt nickel-redox graphene composite material and its application |
| CN112687477A (en) * | 2020-12-10 | 2021-04-20 | 郑州轻工业大学 | Preparation method and application of double-transition metal phosphide graphene composite material CoNiP-rGO |
| CN114959735A (en) * | 2022-04-28 | 2022-08-30 | 东华大学 | Preparation method and application of graphene/nickel cobalt phosphide film |
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| CN112687477A (en) * | 2020-12-10 | 2021-04-20 | 郑州轻工业大学 | Preparation method and application of double-transition metal phosphide graphene composite material CoNiP-rGO |
| CN112687477B (en) * | 2020-12-10 | 2022-05-20 | 郑州轻工业大学 | Preparation method and application of double-transition metal phosphide graphene composite material CoNiP-rGO |
| CN114959735A (en) * | 2022-04-28 | 2022-08-30 | 东华大学 | Preparation method and application of graphene/nickel cobalt phosphide film |
| CN114959735B (en) * | 2022-04-28 | 2023-12-12 | 东华大学 | Preparation method and application of graphene/nickel cobalt phosphide film |
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Application publication date: 20181218 |