CN109778225A - A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation - Google Patents
A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation Download PDFInfo
- Publication number
- CN109778225A CN109778225A CN201910101689.XA CN201910101689A CN109778225A CN 109778225 A CN109778225 A CN 109778225A CN 201910101689 A CN201910101689 A CN 201910101689A CN 109778225 A CN109778225 A CN 109778225A
- Authority
- CN
- China
- Prior art keywords
- mose
- ldh
- cofe
- dispersion liquid
- aeroge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of N, S codope graphenes/MoSe2The preparation method of/CoFe-LDH aeroge, which comprises the following steps: S1 prepares graphene oxide layer dispersion liquid, MoSe respectively2Nanometer sheet dispersion liquid and stratiform CoFe-LDH nanometer sheet dispersion liquid；S2, by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid mixing, is added reducing agent and crosslinking agent, is uniformly mixed, and reacts and N, S codope graphene/MoSe is made2Hydrogel, freeze-drying, obtains N, S codope graphene/MoSe2Aeroge；S3, by the N, S codope graphene/MoSe2Aeroge is immersed in stratiform CoFe-LDH nanometer sheet dispersion liquid, and N, S codope graphene/MoSe is made2/ CoFe-LDH hydrogel is freeze-dried to obtain N, S codope graphene/MoSe2/ CoFe-LDH aeroge.Ternary N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH aeroge has superior liberation of hydrogen and analysis oxygen performance under alkaline condition.
Description
Technical field
The present invention relates to a kind of electrode liberations of hydrogen to analyse oxygen material, and in particular to a kind of N, S codope graphene/MoSe2/
CoFe-LDH and preparation method thereof.
Background technique
Energy and environment are the material bases that human society is depended on for existence and development, and importance is self-evident.In recent years,
With the rapid growth of world population, the acceleration of the energy is consumed, and energy shortage and environmental pollution is led to problems such as to get worse,
Existence and health to the mankind cause huge threat.In consideration of it, need of the mankind to new, sustainable use clean energy resource
Ask extremely urgent.Electro-catalysis water decomposition is efficient one of the important channel for generating renewable and clean energy resource, and decomposition product only has
O2And H2, to zero environmental, and O2And H2It can be used as the raw material of fuel cell again, so water decomposition can guarantee energy benefit
With the green of process, environmental protection.However, during utilization from electrolysis water to hydrogen energy source, how energy saving, reduce cost, most
The technical problem for improving water decomposition efficiency and yield and always perplexing researcher of limits.The cell reaction of water is by analysis oxygen
(OER) it is formed with two half-reactions of liberation of hydrogen (HER), by reducing the energy barrier of half-reaction and improving efficient energy conversion to Guan Chong
It wants.Although noble metal catalyst (such as Pt series catalysts catalytic hydrogen evolution react, Ir series catalysts be catalyzed oxygen evolution reaction) be at present most
Promising water decomposition catalyst, but its at high price and scarcity of resources greatly limits being widely used for they.In recent years,
There is a large amount of research work to report non-precious metal catalyst catalytic decomposition elutriation hydrogen or analysis oxygen, and make some progress,
But these catalyst or be to be catalyzed oxygen evolution reaction or be that catalytic hydrogen evolution is anti-in acidic electrolyte bath in the alkaline electrolyte
It answers, it is not high to the utilization efficiency of water.In view of the practical application of water decomposition, efficient elctro-catalyst must be in identical electrolysis
Catalytic hydrogen evolution reaction simultaneously and oxygen evolution reaction (mainly in alkaline electrolyte) in matter, this is to current many in acidic electrolyte bath
In with high activity catalyst for be still one challenge.Therefore, research and develop it is novel, efficient, can be catalyzed simultaneously
The elctro-catalyst of evolving hydrogen reaction and oxygen evolution reaction has become the key of electro-catalysis water dissociation technology development.
Stratiform transition metal double-hydroxide (Layered double hydroxide, LDH) is a kind of with larger ratio
Surface area can carry out a kind of artificial synthesized stratified material according to specific function.LDH has various unique physics, change
The properties such as property, including laminate electropositive, main element variability, interlamellar spacing adjustability are learned, therefore in catalysis, the energy, Shui Chu
Reason etc. has very big application potential.In recent years, it deepens continuously, finds to the research of LDH structure and performance with people
This kind of material has shown excellent activity in electro-catalysis water decomposition field.Xiang etc. is direct using electrodeposition process at room temperature
ZnCo-LDH film is grown in Ni foil substrate flexible, which contains the nanometer wall construction of oriented growth, to alkaline condition
Lower water decomposition oxygen evolution reaction shows fabulous catalytic activity and durability.Its key factor with high activity is mutually to interconnect
The two-dimentional LDH nanometer sheet connect is vertical-growth on conductive substrate, thus those is made to be conducive to the active site of catalysis reaction
Largely it is exposed.The NiFe-LDH of Li design preparation is the ultrathin nanometer piece obtained by being inserted into molybdate ion.The material
Under alkaline condition, the common NiFe-LDH of the current density ratio of electro-catalysis water decomposition oxygen evolution reaction is higher by 3 times, is primarily due to
This ultra-thin thickness is conducive to make full use of electro-chemical activity site, and then improves catalytic performance.
Transition metal dichalcogenide (molybdenum disulfide (MoS2)), two selenizing molybdenum (MoSe2)) due to unique physics, change
Property is learned, the catalyst of most promising a kind of electro-catalysis water decomposition evolving hydrogen reaction is equally also considered as.It is well known that stratiform
Transition metal dichalcogenide can be stripped into the two-dimensional ultrathin nanoscale twins of similar graphene-structured, this two-dimensional nano piece
Layer has a large amount of active edge site, is conducive to the raising of its electro-catalysis water decomposition evolving hydrogen reaction performance.Cheng etc. is using high
The ultra-thin MoS of warm liquid phase synthesizing method preparation2Thickness and a large amount of edge site of the nanometer sheet with monoatomic layer, so that MoS2It receives
Rice piece has shown excellent evolving hydrogen reaction catalytic activity in acidic electrolyte bath, and stability is good.The passing through such as Fu
Vapour deposition process is learned in SiO2The MoS of single layer has been prepared in/Si substrate2(1-x)Se2x, the MoS of this mono-crystalline structures2(1-x)Se2x
Band gap can by change Se and S ratio be adjusted, make its electrocatalytic hydrogen evolution react activity be optimal, and its
Performance is better than pure single layer MoS2And MoSe2。
Due to superelevation electric conductivity, high-specific surface area, excellent chemistry and environmental stability and strong adsorptivity, stone
Black alkene can be used as a kind of excellent catalyst carrier.Related graphene is self-assembled into the research of three-dimensional grapheme hydrogel
Relatively broad attention is obtained, the fields such as electro-catalysis water decomposition are especially applied to.
Summary of the invention
An object of the present invention is N, S codope graphene/MoSe2/ CoFe-LDH and preparation method thereof.
In order to achieve the above object, the present invention provides a kind of N, S codope graphenes/MoSe2/ CoFe-LDH aeroge
Preparation method, which comprises the following steps:
S1 prepares graphene oxide layer dispersion liquid, MoSe respectively2Nanometer sheet dispersion liquid and stratiform CoFe-LDH nanometer sheet
Dispersion liquid；
S2, by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid mixing, is added reducing agent and crosslinking
Agent is uniformly mixed, and reacts and N, S codope graphene/MoSe is made2Hydrogel, freeze-drying, obtains N, and S codope graphene/
MoSe2Aeroge；
S3, by the N, S codope graphene/MoSe2Aeroge is immersed in stratiform CoFe-LDH nanometer sheet dispersion liquid,
N, S codope graphene/MoSe is made2/ CoFe-LDH hydrogel is freeze-dried to obtain N, S codope graphene/MoSe2/CoFe-
LDH aeroge.
Graphene oxide layer dispersion liquid, the MoSe of the S12Nanometer sheet dispersion liquid and stratiform CoFe-LDH nanometer sheet point
Point of the preparation of dispersion liquid without sequencing, sequentially can arbitrarily convert.
Further, the preparation of the graphene oxide layer dispersion liquid includes surpassing graphite oxide in deionized water
Sound dispersion, is made graphene oxide layer dispersion liquid.
Further, the MoSe2Nanometer sheet dispersion liquid is prepared by liquid phase stripping method.
Further, the stratiform CoFe-LDH nanometer sheet dispersion liquid is prepared by hydro-thermal method.
Further, the graphite oxide is prepared by the following method:
S11, in ice bath, be vigorously stirred under, by NaNO3It is added in the concentrated sulfuric acid, until NaNO3It is completely dissolved；
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath, reaction to reaction are removed after having added
Liquid is in thick；
The deionized water of the first weight is added in S13, and after reacting a period of time, the second weight is added at lower than 120 DEG C
Deionized water；
H is added in S14, room temperature2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating；
S15, the precipitating are washed with HCl solution, and drying obtains graphite oxide.
Further, described that MoSe is prepared by liquid phase stripping method2The specific steps of nanometer sheet dispersion liquid include: by two selenium
Change molybdenum to be added in isopropanol/water mixed solution, MoSe is made in ultrasonic oscillation2Nanometer sheet dispersion liquid.
Further, the specific steps for preparing stratiform CoFe-LDH nanometer sheet dispersion liquid by hydro-thermal method include:
S31, by Co (NO3)2·6H2O、Fe(NO3)3·9H2O, urea and trisodium citrate are dispersed in water, in 130-
170 DEG C of reactions, wash after having reacted, are dried to obtain powdered substance；
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is that CoFe-LDH receives
Rice piece dispersion liquid.
Further, in step S2, the graphene oxide layer and the MoSe2The weight ratio of nanometer sheet be 4:9~
36:1。
Further, in step S3, N, S codope graphene/MoSe2With the weight ratio of the CoFe-LDH be 10:1~
1:10。
Further, the reducing agent is L-cysteine, ascorbic acid, glucose or their any mixing.
Further, the crosslinking agent is L-cysteine and/or polypyrrole.
Further, the step S2 are as follows: by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid
Reducing agent and crosslinking agent is added in mixing, is uniformly mixed, and reacts and N, S codope graphene/MoSe is made2Hydrogel, freezing are dry
It is dry, obtain N, S codope graphene/MoSe2Aeroge.
The present invention also provides N prepared by a kind of above-mentioned preparation method, S codope graphenes/MoSe2/CoFe-
LDH aeroge.
N of the invention, S codope graphene/MoSe2/ CoFe-LDH aeroge can be used as electro-catalysis water decomposition electrode, tool
There is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the overpotential of evolving hydrogen reaction is -237mV, analysis
Oxygen overpotential is 1.59V；It has very big electrolysis water application value, especially liberation of hydrogen under alkaline condition and analysis as electrode
Oxygen performance.
Compared with prior art, the present invention uses graphite oxide, MoSe2, CoFe-LDH be made ternary N, S codope graphite
Alkene/MoSe2/ CoFe-LDH aeroge, has the following beneficial effects:
1) ultra-thin MoSe is prepared with liquid phase stripping method2Nanometer sheet dispersion liquid has the advantages that at low cost, safe operation.
2) L-cysteine makes to be cross-linked with each other between graphene sheet layer to form 3D network structure as crosslinking agent, also as N,
The source S is doped graphene, due to N, S ratio sp2C has bigger electronegativity, improves its electric conductivity.
3) pass through electrostatic interaction for negatively charged N, S codope graphene/MoSe2With positively charged CoFe-LDH's
Self assembly effect is prepared into ternary N, S codope graphene/MoSe2/ CoFe-LDH aerogel composite does not need any severe
The condition at quarter, product structure can easily be accommodated, and batch wise differences are small, be suitble to large-scale production.
4) ternary N produced by the present invention, S codope graphene/MoSe2There is/CoFe-LDH aeroge excellent electricity to urge
Change water dispersible energy, when current density is 100mA/cm2When, the overpotential of evolving hydrogen reaction is -237mV, and overpotential for oxygen evolution is
1.59V；
5) ternary N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH aeroge has under alkaline condition
There are superior liberation of hydrogen and analysis oxygen performance.
Detailed description of the invention
Fig. 1 is the N of one embodiment of the invention, S codope graphene/MoSe2The x-ray powder of/CoFe-LDH aeroge
Diffracting spectrum；
Fig. 2 is the N of one embodiment of the invention, S codope graphene/MoSe2The scanning electron microscope of/CoFe-LDH aeroge
Figure；
Fig. 3 is the partial enlarged view of Fig. 1 scanning electron microscope；
Fig. 4 is the N of one embodiment of the invention, S codope graphene/MoSe2The high-resolution of/CoFe-LDH aeroge transmits
Electronic Speculum；
Fig. 5 is the N of one embodiment of the invention, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode liberation of hydrogen LSV
Polarization curve；
Fig. 6 is the N of one embodiment of the invention, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode liberation of hydrogen
Tafel slope curve figure；
Fig. 7 is the N of one embodiment of the invention, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode analyses oxygen LSV
Polarization curve；
Fig. 8 is the N of one embodiment of the invention, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode analyses oxygen
Tafel slope curve figure；
Fig. 9 is the N of one embodiment of the invention, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode liberation of hydrogen and analysis
The Faradaic efficiency curve of oxygen.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The N of present pre-ferred embodiments, S codope graphene/MoSe2The preparation method of/CoFe-LDH, comprising:
S1, by graphite oxide in deionized water ultrasonic disperse, be made graphene oxide layer dispersion liquid.Preferably, it makes
The concentration of the graphene oxide layer dispersion liquid obtained is 0.5-3mg mL-1, more preferably 2mg mL-1。
Specifically, the graphite oxide is prepared by the following method:
S11, in ice bath, be vigorously stirred under, by NaNO3It is added in the concentrated sulfuric acid, until NaNO3It is completely dissolved.
Such as: the concentrated sulfuric acid (H that concentration is 98% is added into three mouthfuls of reaction flasks2SO4), and reaction flask is placed in ice-water bath
In with 150rpm revolving speed stirring, be added NaNO3, continue stirring under ice-water bath and be allowed to dissolve.Wherein, the concentrated sulfuric acid and NaNO3's
Weight ratio are as follows: 60:1~100:1.
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath, reaction to reaction are removed after having added
Liquid is in thick.
Such as: it maintains ice-water bath constant, natural graphite powder is added, by KMnO4It is slowly added in batches, keeps reaction temperature control
System continues to stir in ice-water bath no longer to rise to temperature at 10 DEG C or less (more preferably 5 DEG C or less) after addition.So
Deicing water-bath is moved back, it is in sticky ink that reaction flask is placed in reaction to reaction solution in the water-bath of 25-45 DEG C (more preferably 35 DEG C)
Green.Wherein: NaNO3, graphite powder, KMnO4Weight ratio are as follows: (0.5-1.5): (1-3): (4-8).
The deionized water of the first weight is added in S13, and after reacting a period of time, the second weight is added at lower than 120 DEG C
Deionized water.Preferably, first weight is 1.5-2.5 times of concentrated sulfuric acid volume, and second weight is reaction solution volume
2-4 times.
Such as: the deionized water of the first weight is added, control reaction temperature is lower than 98 DEG C, under oil bath, reaction a period of time
Afterwards, the deionized water of 1.5 times of reaction solution or more weight is added at 98 DEG C.
The present embodiment controls reaction solution in slight boiling condition, after concentrated sulfuric acid system being added to avoid deionized water, body
It is that heat release is more violent, it is more dangerous after generation splash phenomena, especially iodine, so in order to ensure security control reaction
System is slightly boiled, and temperature is not easy more than 98 DEG C.
S14, room temperature are slowly added to H2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating.
Such as: at room temperature, it is slowly added to 30wt%H2O2Aqueous solution, after stirring a period of time, after the reaction was completed, in centrifugation
It is centrifuged in machine, outwells supernatant liquor, retain precipitating.
S15, the precipitating are washed with HCl solution, dry to obtain graphite oxide.
Such as: precipitating is washed into centrifugation several times with 10wt%HCl solution, then is washed with deionized to supernatant liquor
PH is most neutral, and sediment is dried to obtain solid oxidation graphite in 50-90 DEG C of baking oven.
S2 prepares ultra-thin MoSe by liquid phase stripping method2Nanometer sheet dispersion liquid.
Such as: two selenizing molybdenum of block is dispersed in isopropanol/water mixed solution, ultra-thin MoSe is made in ultrasonic oscillation2
Nanometer sheet dispersion liquid.In one embodiment, two selenizing molybdenum of block is dispersed in isopropanol/water (V/V, 6/4) mixed solution
In, ultra-thin two selenizings molybdenum (MoSe was removed by 300W ultrasonic oscillation 2-4 hours2) nanometer sheet dispersion liquid.Preferably,
The MoSe2Nanometer sheet dispersion liquid concentration is 0.2-1.0mg mL-1；More preferably 0.5mg mL-1。
The embodiment of the present invention prepares ultra-thin MoSe using liquid phase stripping method2Nanometer sheet dispersion liquid, at low cost, operation peace
Entirely.
S3 prepares stratiform CoFe-LDH nanometer sheet dispersion liquid by hydro-thermal method；Preferably, CoFe-LDH nanometer sheet dispersion liquid
Concentration be (0.5-2) mg.ml-1；More preferably are as follows: 1mg.ml-1。
Specifically,
S31, by Co (NO3)2·6H2O、Fe(NO3)3·9H2O, urea, trisodium citrate are dispersed in water, in 130-170
DEG C reaction, react after washing, dry powdered substance.More specifically, being (7-12): (1-4): (2-6): 1 by weight ratio
Co (NO3)2·6H2O、Fe(NO3)3·9H2O, urea, trisodium citrate are scattered in distilled water, and ultrasound is until clarification, Yu Han
Have in the stainless steel hydrothermal reaction kettle of polytetrafluoroethylsubstrate substrate, seal, reacted at 130-170 DEG C, filtered after react, with water and
Ethanol washing is multiple, is dried in vacuo obtained powdered substance.
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is that CoFe-LDH receives
Rice piece dispersion liquid.Specifically, it disperses step S31 powdered substance in and carries out being ultrasonically treated in the formamide solution of degassing
To suspension, centrifugation removes unstripped block, taking supernatant to obtain supernatant is CoFe-LDH nanometer sheet dispersion liquid.
Point of above step S1, S2, S3 out-of-order, three sequence of steps can be converted arbitrarily.
S4, by the graphene oxide layer dispersion liquid and MoSe2Reducing agent, crosslinking is added in nanometer sheet dispersion liquid mixing
Agent is uniformly mixed, and reacts and N, S codope graphene/MoSe is made2Hydrogel, freeze-drying, obtains N, and S codope graphene/
MoSe2Aeroge.
Preferably, the step S4 includes: by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid
Mixing is added reducing agent, crosslinking agent, pH adjusting agent and stirs evenly, reacts and N, S codope graphene/MoSe is made2Hydrogel,
Freeze-drying, obtains N, S codope graphene/MoSe2Aeroge.
Wherein, the graphene oxide layer and the MoSe2The weight ratio of nanometer sheet is 4:9~36:1.The reduction
Agent is L-cysteine, ascorbic acid, glucose or their any mixing.The crosslinking agent is L-cysteine and/or gathers
Pyrroles.The pH adjusting agent is the ammonium hydroxide that concentration is 25-28wt%, and dosage is graphene oxide layer dispersion liquid volume
0.05~0.1 times.
In the present embodiment, pH adjusting agent is used to adjust the pH value of solution as 9-11, to influence graphene oxide sheet
The potential of layer surface influences redox graphene in the solution poly- using the electrostatic repulsion between graphene oxide layer
Collection state.And then it is not necessarily to stabilizer, it can also be made that reducing degree is preferable, the good graphene of dispersion degree.
In a specific embodiment, the reducing agent and crosslinking agent are L-cysteine, are made using L-cysteine
Make to be cross-linked with each other between graphene sheet layer to form 3D network structure for crosslinking agent, be alternatively arranged as the source N, S and graphene is doped,
Due to N, S ratio sp2C has bigger electronegativity, improves its electric conductivity.
S5, by the N, S codope graphene/MoSe2Aeroge is immersed in CoFe-LDH nanometer sheet dispersion liquid, is made
N, S codope graphene/MoSe2/ CoFe-LDH hydrogel is freeze-dried to obtain N, S codope graphene/MoSe2/CoFe-LDH
Aeroge；Wherein, N, S codope graphene/MoSe2Weight ratio with the CoFe-LDH is 10:1~1:10.
N after freeze-drying, S codope graphene/MoSe2After being added in CoFe-LDH nanometer sheet dispersion liquid, by
Positively charged CoFe-LDH nanometer sheet is made to be adsorbed on negatively charged N in electrostatic adsorption, S codope graphene/
MoSe2Surface is self-assembly of N, S codope graphene/MoSe2/ CoFe-LDH hydrogel composite material, after freeze-drying
N, S codope graphene/MoSe2/ CoFe-LDH composite aerogel.
Method of the invention is by N, S codope graphene, MoSe2, tri- kinds of layered catalytic Material claddings of CoFe-LDH, be made
N, S codope graphene/MoSe2/ CoFe-LDH composite aerogel as electro-catalysis water decomposition electrode there is excellent electricity to urge
Change water dispersible energy, as shown in figs. 4 and 6, when current density is 100mA/cm2When, the overpotential of evolving hydrogen reaction is -237mV,
Overpotential for oxygen evolution is 1.59V；It has a very big electrolysis water application value as electrode, liberation of hydrogen especially under alkaline condition and
Analyse oxygen performance and service life, performance is close to commercialized noble metal platinum and iridium catalyst.In addition, N of the invention, S are total
Doped graphene/MoSe2/ CoFe-LDH composite aerogel has very big specific surface area, and since N, S adulterate graphene
Make it have extraordinary electronic conduction ability.
Graphite oxide in following specific embodiments is made by the following method:
The 46mL concentrated sulfuric acid (98%H is added into three mouthfuls of reaction flasks2SO4), and reaction flask is placed in ice-water bath with 150rpm
Revolving speed stirring, then weighs 1g NaNO3It is added in reaction flask, continues to stir 10min under ice-water bath, until NaNO3It is completely dissolved,
It maintains ice-water bath constant, then weighs the addition of 2g natural graphite powder, weigh 6g KMnO4It is slowly added in batches, keeps reaction temperature control
It makes at 5 DEG C hereinafter, continuing the stirring 30min in ice-water bath after addition and no longer rises to temperature.Then ice-water bath is removed, it will
Reaction flask, which is placed in 35 ± 3 DEG C of water-bath, to react 1 hour, and reaction solution is slowly added to 92mL deionized water, instead in sticky blackish green
Answer system temperature to increase, control temperature does not exceed 98 DEG C, and 15min is reacted under 98 DEG C of oil baths, be added while hot 300mL go from
Sub- water, removes oil bath, drops to room temperature to reacting liquid temperature, 10mL 30%H is added2O2Aqueous solution (is slowly added to), continues to stir
Reaction 1 hour is centrifuged with the centrifuge that revolving speed is 5000r min-1 after the reaction was completed, outwells supernatant liquor, retains lower sediment
Centrifugation is washed with 10wt%HCl solution again, centrifugation is finally washed with deionized in repeated washing centrifugation 10 times, until upper layer is clear
Liquid pH value is neutrality.Obtained sediment is dried overnight in 80 DEG C of baking oven, obtains solid oxidation graphite.
Two selenizing molybdenum (MoSe used in following embodiment2) be purchased from Mike woods company, purity 99.8%, No. MDL:
MFCD00049703。
Embodiment 1
A kind of N, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, comprising:
(1) it the preparation of graphene oxide (GO) lamella dispersion liquid: disperses 200mg graphite oxide obtained above in
In 100mL deionized water, ultrasonic disperse 1 hour, the GO lamella dispersion liquid of sepia is obtained, GO concentration is 2mg mL-1。
(2) liquid phase stripping method prepares ultra-thin MoSe2The preparation of nanometer sheet dispersion liquid: by 20mg block MoSe24mL body is added
Isopropanol (IPA)/water in the mixed solvent that fraction is 60%, puts it into Ultrasound Instrument with the power of 200W and 40kHz
Frequency carry out ultrasonic oscillation handle 4 hours, by be added recirculated cooling water keep ultrasonic procedure in temperature control in room temperature.
Then, the solution after ultrasound is centrifuged 20 minutes with the speed of 4000rpm, the unstripped block MoSe in removal bottom2, obtain
Layer clear liquid is two dimension MoSe2Nanometer sheet, testing its concentration is about 0.5mgmL-1, spare.
(3) preparation of stratiform CoFe-LDH nanometer sheet dispersion liquid: by 0.27g Co (NO3)2·6H2O, 0.09g Fe
(NO3)3·9H2O, 0.12g urea and 0.03g trisodium citrate are dispersed in 75mL distilled water, ultrasonic treatment about 30min until
Clarification.Obtained solution is transferred in the stainless steel hydrothermal reaction kettle containing polytetrafluoroethylsubstrate substrate, is sealed, and at 150 DEG C
Heating reaction 20 hours.After being cooled to room temperature, solid product is collected by filtration, it is multiple with distilled water and ethanol washing respectively, and
Be dried in vacuo 8 hours at 60 DEG C and obtain powdered substance, add it to 50mL degassing formamide solution (50wt%) in into
Row ultrasonic treatment obtains suspension, then, is centrifuged 20 minutes with the speed of 4000rpm to remove unstripped block materials, takes
Supernatant is stratiform CoFe-LDH nanometer sheet dispersion liquid, concentration 1mg/mL.
(4) by 5mL graphene oxide layer dispersion liquid (the 2.0mg mL-1) and 5mL MoSe2Nanometer sheet dispersion liquid
(0.5mg mL-1) mixing, by 50mg L-cysteine and 300 μ L NH3·H2O (25-28wt%) is added gradually to 5mL GO
(2.0mg mL-1) and 5mL MoSe2(0.5mg mL-1) mixed solution in, then ultrasonic mixing is uniform.Resulting mixing is molten
Liquid is transferred in the stainless steel hydrothermal reaction kettle containing polytetrafluoroethylsubstrate substrate, sealing, and heating reaction 3 hours at 180 DEG C.
Cooled to room temperature obtains N, S codope graphene (N, S-rGO)/MoSe2Hydrogel.Then, by N, S-rGO/MoSe2Water
Gel is washed with distilled water for several times, and then freeze-drying obtains N, S-rGO/MoSe2Aeroge.
(5) N for obtaining 10mg, S codope graphene/MoSe2Aeroge is immersed in CoFe-LDH nanometers of 10mL stratiform
Piece dispersion liquid (1mg mL-1) in, it impregnates for 24 hours so that stratiform CoFe-LDH nanometer sheet is adsorbed on N by electrostatic self-assembled, S is co-doped with
Miscellaneous graphene/MoSe2On reach balance.Hereafter, by the N of acquisition, S codope graphene/MoSe2/ stratiform CoFe-LDH Compound Water
Gel is washed with distilled water for several times, is then freeze-dried, and N, S codope graphene/MoSe are obtained2The CoFe-LDH airsetting of/stratiform
Glue.Fig. 1 is N, S codope graphene/MoSe2The X-ray powder diffraction pattern of/CoFe-LDH aeroge.
Performance test:
By N obtained, S codope graphene/MoSe2/ CoFe-LDH aeroge scanning electron microscope (SEM), height
The test of resolved transmittance Electronic Speculum.As can be seen from Figure 2, N obtained, S codope graphene/MoSe2/ CoFe-LDH aeroge forms 3D
Cellular structure, duct N, S codope graphene/MoSe2/ CoFe-LDH aeroge, and from Fig. 3,4 it is found that N, S codope stone
Black alkene, MoSe2And tri- kinds of elementary materials of CoFe-LDH are effectively compound, form stable trielement composite material.
Fig. 5 is N, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode liberation of hydrogen LSV polarization curve, tri compound
Material has excellent Hydrogen Evolution Performance, and overpotential is smaller, and current density is more negative, illustrates that Hydrogen Evolution Performance is better.
Fig. 6 is N, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode liberation of hydrogen Tafel slope curve figure, from figure
6 it is found that N, S codope graphene/MoSe2/ CoFe-LDH aeroge Hydrogen Evolution Performance is excellent, and the slope of curve is smaller, illustrates performance
Better.
Fig. 7 is N, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode analyses oxygen LSV polarization curve.It can from Fig. 7
Know, N, S codope graphene/MoSe2/ CoFe-LDH aeroge has excellent analysis oxygen performance, and overpotential is smaller, current density
It is bigger, illustrate that analysis oxygen performance is better.
Fig. 8 is N, S codope graphene/MoSe2/ CoFe-LDH silica aerogel electrode analyses oxygen Tafel slope curve figure.From figure
8 it is found that N, S codope graphene/MoSe2/ CoFe-LDH aeroge analysis oxygen is had excellent performance, and the slope of curve is smaller, illustrates performance
Better.
Fig. 9 is N, S codope graphene/MoSe2The Faradaic efficiency of/CoFe-LDH silica aerogel electrode liberation of hydrogen and analysis oxygen
Curve.As can be seen from Figure 9, N, S codope graphene/MoSe2The practical liberation of hydrogen of/CoFe-LDH aeroge and analysis oxygen efficiency and theoretical value
It is close.
Embodiment 2
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the reduction in embodiment 1
Agent is ascorbic acid, and crosslinking agent is polypyrrole.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, as shown in Fig. 5-8, when current density is 100mA/cm2When,
The overpotential of evolving hydrogen reaction is -290mV, and the overpotential of oxygen evolution reaction is 1.65V.
Embodiment 3
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the reduction in embodiment 1
Agent changes glucose into, and crosslinking agent is polypyrrole.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, as shown in Fig. 5-8, when current density is 100mA/cm2When,
The overpotential of evolving hydrogen reaction is -271mV, and the overpotential of oxygen evolution reaction is 1.84V.
Embodiment 4
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the crosslinking in embodiment 1
Agent changes polypyrrole into, and reducing agent is polypyrrole.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, as shown in Fig. 5-8, when current density is 100mA/cm2When,
The overpotential of evolving hydrogen reaction is -349mV, and the overpotential of oxygen evolution reaction is 1.93V.
Embodiment 5
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the concentration of GO dispersion liquid
For 3mg/mL, MoSe2The concentration of nanometer sheet dispersion liquid is 1mg/mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -317mV, and the overpotential of oxygen evolution reaction is 1.63V
Embodiment 6
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that the concentration of GO dispersion liquid
For 0.5mg/mL, the concentration of stratiform CoFe-LDH nanometer sheet dispersion liquid is 0.5mg/mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -417mV, and the overpotential of oxygen evolution reaction is 1.64V.
Embodiment 7
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO dispersion liquid (concentration
Volume 2.0mg/mL) is 1mL, MoSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 9mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -369mV, and the overpotential of oxygen evolution reaction is 1.78V.
Embodiment 8
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 1mL, MoSe2The concentration of nanometer sheet dispersion liquid is 0.2mg/mL, volume 6mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -359mV, and the overpotential of oxygen evolution reaction is 1.83V.
Embodiment 9
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 1mL, MoSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 3mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -324mV, and the overpotential of oxygen evolution reaction is 1.75V.
Embodiment 10
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 3mL, MoSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -316mV, and the overpotential of oxygen evolution reaction is 1.98V.
Embodiment 11
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 6mL, MoSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL.
Embodiment 12
The present embodiment and embodiment 1 react and operating condition is essentially identical, the difference is that GO (2.0mg/mL) points
The volume of dispersion liquid is 9mL, MoSe2The volume of nanometer sheet dispersion liquid (0.5mg/mL) is 1mL, CoFe-LDH nanometer sheet dispersion liquid
Concentration is 2mg/mL.
After tested, N produced by the present invention, S codope graphene/MoSe2/ CoFe-LDH composite aerogel is urged as electricity
Change water decomposition electrode, there is excellent electro-catalysis water dispersible energy, when current density is 100mA/cm2When, the mistake of evolving hydrogen reaction
Current potential is -379mV, and the overpotential of oxygen evolution reaction is 1.86V.
The above is only some embodiments of the invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of N, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, which is characterized in that including following step
It is rapid:
S1 prepares graphene oxide layer dispersion liquid, MoSe respectively2Nanometer sheet dispersion liquid and the dispersion of stratiform CoFe-LDH nanometer sheet
Liquid；
S2, by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid mixing, is added reducing agent and crosslinking agent, mixes
It closes uniformly, reacts and N, S codope graphene/MoSe is made2Hydrogel, freeze-drying, obtains N, S codope graphene/MoSe2
Aeroge；
S3, by the N, S codope graphene/MoSe2Aeroge is immersed in stratiform CoFe-LDH nanometer sheet dispersion liquid, is made
N, S codope graphene/MoSe2/ CoFe-LDH hydrogel is freeze-dried to obtain N, S codope graphene/MoSe2/CoFe-LDH
Aeroge.
2. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In, the preparation of the graphene oxide layer dispersion liquid include by graphite oxide in deionized water ultrasonic disperse, oxygen is made
Graphite alkene lamella dispersion liquid.
3. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In the graphite oxide is prepared by the following method:
S11, in ice bath, be vigorously stirred under, by NaNO3It is added in the concentrated sulfuric acid, until NaNO3It is completely dissolved；
S12 maintains ice bath, and graphite powder is added, KMnO is then added portionwise4, ice bath is removed after having added, reaction to reaction solution is in
It is thick；
The deionized water of the first weight is added in S13, after reacting a period of time, in lower than be added at 120 DEG C the second weight go from
Sub- water；
H is added in S14, room temperature2O2Aqueous solution, after the reaction was completed, centrifugation remove supernatant, retain precipitating；
S15, the precipitating are washed with HCl solution, and drying obtains graphite oxide.
4. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In described to prepare MoSe by liquid phase stripping method2The specific steps of nanometer sheet dispersion liquid include: that isopropyl is added in two selenizing molybdenums
In alcohol/water mixed solution, MoSe is made in ultrasonic oscillation2Nanometer sheet dispersion liquid.
5. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In the specific steps for preparing stratiform CoFe-LDH nanometer sheet dispersion liquid by hydro-thermal method include:
S31, by Co (NO3)2·6H2O、Fe(NO3)3·9H2O, urea and trisodium citrate are dispersed in water, in 130-170 DEG C
Reaction, washs after having reacted, is dried to obtain powdered substance；
Powdered substance described in step S31 is dispersed formamide solution by S32, and taking supernatant is CoFe-LDH nanometer sheet
Dispersion liquid.
6. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In, in step S2, the graphene oxide layer and the MoSe2The weight ratio of nanometer sheet is 4:9~36:1.
7. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In, in step S3, N, S codope graphene/MoSe2Weight ratio with the CoFe-LDH is 10:1~1:10.
8. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In the reducing agent is L-cysteine, ascorbic acid, glucose or their any mixing；The crosslinking agent is half Guang of L-
Propylhomoserin and/or polypyrrole.
9. N as described in claim 1, S codope graphene/MoSe2The preparation method of/CoFe-LDH aeroge, feature exist
In the step S2 are as follows: by the graphene oxide layer dispersion liquid and MoSe2Nanometer sheet dispersion liquid mixing, is added reduction
Agent and crosslinking agent are uniformly mixed, and react and N, S codope graphene/MoSe is made2Hydrogel, freeze-drying, obtains N, S is co-doped with
Miscellaneous graphene/MoSe2Aeroge.
10. N prepared by preparation method of any of claims 1-9, S codope graphene/MoSe2/CoFe-LDH
Aeroge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910101689.XA CN109778225B (en) | 2019-01-31 | 2019-01-31 | N, S co-doped graphene/molybdenum selenide/CoFe-LDH aerogel and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910101689.XA CN109778225B (en) | 2019-01-31 | 2019-01-31 | N, S co-doped graphene/molybdenum selenide/CoFe-LDH aerogel and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109778225A true CN109778225A (en) | 2019-05-21 |
| CN109778225B CN109778225B (en) | 2021-08-17 |
Family
ID=66504027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910101689.XA Active CN109778225B (en) | 2019-01-31 | 2019-01-31 | N, S co-doped graphene/molybdenum selenide/CoFe-LDH aerogel and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109778225B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110563051A (en) * | 2019-08-26 | 2019-12-13 | 江苏大学 | Preparation method and application of NiCoAl-LDH/N-GO composite material |
| CN110600273A (en) * | 2019-09-03 | 2019-12-20 | 滨州学院 | Doped transition metal selenide/ordered porous graphene aerogel composite electrode material and preparation method thereof |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN111841582A (en) * | 2020-07-22 | 2020-10-30 | 华中科技大学 | Preparation method and application of cobalt-nickel-based selenide material with dodecahedron-like hollow structure |
| CN112076765A (en) * | 2019-06-12 | 2020-12-15 | 中南大学 | Diselenide/layered double hydroxide composite water electrolysis catalytic material and preparation method and application thereof |
| CN112174127A (en) * | 2020-09-29 | 2021-01-05 | 江苏福瑞士电池科技有限公司 | Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application |
| CN112697853A (en) * | 2020-12-03 | 2021-04-23 | 盐城工学院 | Reduced graphene oxide modified electrode and preparation method and application thereof |
| CN113735180A (en) * | 2021-08-18 | 2021-12-03 | 浙江理工大学 | Method for preparing sodium-ion battery anode material by using cobalt-iron sulfide obtained from LDH-based precursor |
| CN114855191A (en) * | 2022-06-14 | 2022-08-05 | 江苏盛剑环境设备有限公司 | Electrocatalyst for preparing hydrogen peroxide by oxygen reduction and preparation method and application thereof |
| US11437199B1 (en) | 2022-04-08 | 2022-09-06 | King Fahd University Of Petroleum And Minerals | Layered dual hydroxide (LDH) composite |
| CN115094476A (en) * | 2022-07-11 | 2022-09-23 | 南京师范大学 | Co 9 S 8 /Co 3 S 4 /Cu 2 S hybrid nano material and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN105642364A (en) * | 2016-01-22 | 2016-06-08 | 济南大学 | Compound photocatalyst and preparing method and application thereof |
| CN105712303A (en) * | 2016-01-22 | 2016-06-29 | 复旦大学 | Molybdenum selenide nanosheet/fiber-based carbon aerogel composite material and preparation method thereof |
| CN106025210A (en) * | 2016-06-06 | 2016-10-12 | 复旦大学 | Molybdenum selenide/graphene/carbon nanotube composite material and preparation method thereof |
| CN106334501A (en) * | 2016-09-07 | 2017-01-18 | 中南大学 | Three-dimensional N/S double-doped graphene aerogel as well as preparation method and application thereof |
| CN106987857A (en) * | 2017-03-09 | 2017-07-28 | 陕西科技大学 | Single-layer metal structure molybdenum disulfide/redox graphene complex and preparation method thereof |
| CN107670679A (en) * | 2017-09-18 | 2018-02-09 | 江苏大学 | A kind of MoS2The preparation method and applications of/rGO CN composites |
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108823591A (en) * | 2018-06-21 | 2018-11-16 | 肇庆市华师大光电产业研究院 | A kind of ferronickel connection selenium compound and its preparation method and application |
| CN109023416A (en) * | 2018-07-18 | 2018-12-18 | 江苏大学 | The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel |
| CN109205596A (en) * | 2018-10-26 | 2019-01-15 | 上海应用技术大学 | A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation |
-
2019
- 2019-01-31 CN CN201910101689.XA patent/CN109778225B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN105642364A (en) * | 2016-01-22 | 2016-06-08 | 济南大学 | Compound photocatalyst and preparing method and application thereof |
| CN105712303A (en) * | 2016-01-22 | 2016-06-29 | 复旦大学 | Molybdenum selenide nanosheet/fiber-based carbon aerogel composite material and preparation method thereof |
| CN106025210A (en) * | 2016-06-06 | 2016-10-12 | 复旦大学 | Molybdenum selenide/graphene/carbon nanotube composite material and preparation method thereof |
| CN106334501A (en) * | 2016-09-07 | 2017-01-18 | 中南大学 | Three-dimensional N/S double-doped graphene aerogel as well as preparation method and application thereof |
| CN106987857A (en) * | 2017-03-09 | 2017-07-28 | 陕西科技大学 | Single-layer metal structure molybdenum disulfide/redox graphene complex and preparation method thereof |
| CN107670679A (en) * | 2017-09-18 | 2018-02-09 | 江苏大学 | A kind of MoS2The preparation method and applications of/rGO CN composites |
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108823591A (en) * | 2018-06-21 | 2018-11-16 | 肇庆市华师大光电产业研究院 | A kind of ferronickel connection selenium compound and its preparation method and application |
| CN109023416A (en) * | 2018-07-18 | 2018-12-18 | 江苏大学 | The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel |
| CN109205596A (en) * | 2018-10-26 | 2019-01-15 | 上海应用技术大学 | A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076765A (en) * | 2019-06-12 | 2020-12-15 | 中南大学 | Diselenide/layered double hydroxide composite water electrolysis catalytic material and preparation method and application thereof |
| CN110563051A (en) * | 2019-08-26 | 2019-12-13 | 江苏大学 | Preparation method and application of NiCoAl-LDH/N-GO composite material |
| CN110600273A (en) * | 2019-09-03 | 2019-12-20 | 滨州学院 | Doped transition metal selenide/ordered porous graphene aerogel composite electrode material and preparation method thereof |
| CN110600273B (en) * | 2019-09-03 | 2021-05-14 | 滨州学院 | Preparation method of doped selenide/graphene aerogel composite electrode material |
| CN110563960B (en) * | 2019-09-16 | 2021-04-02 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110614105B (en) * | 2019-09-25 | 2022-05-31 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN111841582A (en) * | 2020-07-22 | 2020-10-30 | 华中科技大学 | Preparation method and application of cobalt-nickel-based selenide material with dodecahedron-like hollow structure |
| CN112174127A (en) * | 2020-09-29 | 2021-01-05 | 江苏福瑞士电池科技有限公司 | Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application |
| CN112697853A (en) * | 2020-12-03 | 2021-04-23 | 盐城工学院 | Reduced graphene oxide modified electrode and preparation method and application thereof |
| CN113735180A (en) * | 2021-08-18 | 2021-12-03 | 浙江理工大学 | Method for preparing sodium-ion battery anode material by using cobalt-iron sulfide obtained from LDH-based precursor |
| CN113735180B (en) * | 2021-08-18 | 2023-08-22 | 凡尔钠(上海)电池技术有限公司 | Method for preparing sodium ion battery anode material by using LDH-based precursor to obtain cobalt iron sulfide |
| US11437199B1 (en) | 2022-04-08 | 2022-09-06 | King Fahd University Of Petroleum And Minerals | Layered dual hydroxide (LDH) composite |
| CN114855191A (en) * | 2022-06-14 | 2022-08-05 | 江苏盛剑环境设备有限公司 | Electrocatalyst for preparing hydrogen peroxide by oxygen reduction and preparation method and application thereof |
| CN115094476A (en) * | 2022-07-11 | 2022-09-23 | 南京师范大学 | Co 9 S 8 /Co 3 S 4 /Cu 2 S hybrid nano material and preparation method and application thereof |
| CN115094476B (en) * | 2022-07-11 | 2023-09-22 | 南京师范大学 | Co (cobalt) 9 S 8 /Co 3 S 4 /Cu 2 S-hybridized nano material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109778225B (en) | 2021-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109778225A (en) | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation | |
| Yang et al. | Hierarchical spheres constructed by defect-rich MoS2/carbon nanosheets for efficient electrocatalytic hydrogen evolution | |
| Zhang et al. | Heteroatom embedded graphene-like structure anchored on porous biochar as efficient metal-free catalyst for ORR | |
| CN106158405B (en) | A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor | |
| Chen et al. | N-doped 3D porous carbon catalyst derived from biowaste Triarrhena sacchariflora panicle for oxygen reduction reaction | |
| Abrishamkar et al. | Nano-ZSM-5 zeolite: synthesis and application to electrocatalytic oxidation of ethanol | |
| CN107010670A (en) | A kind of MoSxOy/ carbon nano-composite material, its preparation method and its application | |
| CN105140046B (en) | A kind of nanometer of γ-MnO2The preparation method and applications of/graphene aerogel composite material | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN108364793A (en) | CoNiFe-LDH/ multi-layer graphene high-performance composite energy-storage materials and preparation method thereof | |
| CN109205596A (en) | A kind of graphene/WSe2/ NiFe-LDH aeroge and its preparation | |
| CN109546162A (en) | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material | |
| CN110292939B (en) | Double-carbon-limited-domain iridium nanocluster and preparation method and application thereof | |
| CN110368960A (en) | A kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material | |
| CN113816437B (en) | Preparation method of oxygen reduction catalyst of dimethyl imidazole cobalt combined nickel-aluminum layered double hydroxide/graphene oxide | |
| CN110124687A (en) | A kind of preparation method of the LDH/rGO composite material of ruthenium doping and its application on evolving hydrogen reaction | |
| Shao et al. | Hierarchical porous carbons as a metal-free electrocatalyst of triiodide reduction for dye-sensitized solar cells | |
| Wang et al. | A facile strategy to fabricate nitrogen-doped graphene aerogel-supported Fe 3 N nanoparticles as efficient electrocatalysts for the oxygen reduction reaction | |
| Jiang et al. | Biomass-derived porous graphitic carbon with excellent electrocatalytic performances for vanadium redox reactions | |
| Jiang et al. | Fungi-derived, functionalized, and wettability-improved porous carbon materials: an excellent electrocatalyst toward VO2+/VO2+ redox reaction for vanadium redox flow battery | |
| CN109876833A (en) | Nickel oxide loaded sulphur phosphorus doping graphene composite electrocatalyst and preparation method thereof | |
| CN105664969A (en) | Titanium dioxide-platinum-tricobalt tetraoxide tri-element composite photocatalytic material and preparation method thereof | |
| CN114284515A (en) | Ternary heterostructure FePc/Ti3C2/g-C3N4Preparation method and application of composite material | |
| Fu et al. | N-doped hollow carbon tubes derived N-HCTs@ NiCo2O4 as bifunctional oxygen electrocatalysts for rechargeable Zinc-air batteries | |
| CN108043437A (en) | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |