CN107321379A - A kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound and its preparation method and purposes - Google Patents
A kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound and its preparation method and purposes Download PDFInfo
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- CN107321379A CN107321379A CN201710683616.7A CN201710683616A CN107321379A CN 107321379 A CN107321379 A CN 107321379A CN 201710683616 A CN201710683616 A CN 201710683616A CN 107321379 A CN107321379 A CN 107321379A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002096 quantum dot Substances 0.000 title claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 20
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000006260 foam Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 241000219109 Citrullus Species 0.000 claims description 3
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910005855 NiOx Inorganic materials 0.000 description 4
- -1 graphite Alkene Chemical class 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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 invention discloses a kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound, described compound is using nickel foam as matrix, a large amount of micron-sized holes have been etched in nickel foam surface oxidation, retain the three-dimensional porous structure of nickel foam simultaneously, and in foam nickel surface formation nickel oxide and nitrogen-doped graphene quantum dot compound.The compound shows superior electrocatalysis characteristic in alkaline system to oxygen evolution reaction, significantly reduces the overpotential of electrolysis water oxygen evolution reaction.The invention discloses its preparation method.
Description
Technical field
The present invention relates to electro-catalysis energy field, and in particular to a kind of oxide etch technology, in catalyst surface etched hole
Hole, and nickel oxide and nitrogen-doped graphene quantum dot are combined to the electrocatalysis for obtaining composite for lifting oxygen evolution reaction
Energy.
Background technology
At present, as drastically consuming for fossil fuel is increasingly serious with environmental pollution, mankind's active demand is recyclable again
Raw clean energy resource.Hydrogen Energy, is used as the carrier of energy most convenient, it is considered to be one of optimal clean energy resource.Electrolysis water is
Produce one of effective ways of high-purity hydrogen, i.e., apply applied voltage in electrolytic cell, water decompose reaction produce hydrogen with
Oxygen.Wherein, in hydrolysis precipitated oxygen half-reaction (OER), due to its multielectron transfer process, cause dynamic process
It is slow, it is necessary to apply larger external voltage the reaction to be driven to occur, and then cause the cost of electrolytic water device higher and limit
The extensive development of the technology is made.
By selecting suitable oxygen evolution reaction catalysts to be effectively reduced oxygen evolution reaction applied voltage.To being at present
Only, the OER elctro-catalysts of commercial applications are mainly iridium/ru oxide, but the scarcity of these precious metal materials and
High price seriously hinders their extensive use.Therefore, by the exploitation and exploration of various technologies, development is efficient, non-noble gold
Category OER elctro-catalysts have important actual application value.
In recent decades, researchers, which have developed a variety of base metal nickel-base materials with greater activity, is used for electro-catalysis
OER, such as nickel-based oxide, hydroxide, sulfide, phosphide, nitride.But the Ni-based elctro-catalyst developed at present
Electro catalytic activity and stability still can not be compared favourably with noble metal electrocatalyst.Research shows, is set by certain material
Meter and modification strategies can effectively lift electrocatalysis characteristic, and such as electro catalytic activity component is combined to be lifted with conductive matrices and led
Electrically, a variety of electro-chemical activity components are compound can increase electro catalytic activity site, control and prepare three-dimensional porous structure and can increase
Specific surface area etc..But, structure, composition and the electrocatalysis characteristic of accuracy controlling target elctro-catalyst are still more difficult, and this is needed
Researchers are wanted constantly to explore and summarize.
The content of the invention
In order to realize that increase pore space structure lifts the target of elctro-catalyst performance, the present invention proposes one kind oxide etch
The method that technology prepares porous oxidation nickel material, and the preferable nitrogen-doped graphene quantum dot of composite conducting performance further increases
Avtive spot is to lift electro-catalysis OER performances.The generation of oxide etch and the compound of nitrogen-doped graphene quantum dot are three
In situ, synchronous realization in nickel foam matrix is tieed up, resulting combined oxidation nickel material is shown efficiently in alkaline system to OER
Electro catalytic activity and stiff stability.
Technical scheme is as follows：
A kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound, described compound be using nickel foam as
Matrix, a large amount of micron-sized holes have been etched in nickel foam surface oxidation, while retain the three-dimensional porous structure of nickel foam, and
In foam nickel surface formation nickel oxide and nitrogen-doped graphene quantum dot compound.
The preparation method of a kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound, it is by the following steps group
Into：
Step 1. is respectively adopted ethanol, secondary water and is cleaned by ultrasonic nickel foam 30 minutes, is then placed on 40 DEG C of vacuum and does
Dried in dry case stand-by；
Step 2. prepares nitrogen-doped graphene quantum dot using improved microwave process for synthesizing, i.e., using biomass watermelon flesh
For carbon source and nitrogen source, obtained by the process processing such as hydro-thermal, dialysis, pyrolysis, microwave, purifying, quantitative【Referring to：Lv J-J, Zhao
J, Fang H, Jiang L-P, Li L-L, Ma J*, and Zhu J-J*, Incorporating Nitrogen-Doped
Graphene Quantum Dots and Ni3S2Nanosheets：A Synergistic Electrocatalyst with
Highly Enhanced Activity for Overall Water Splitting, Small, 2017,13 (24),
1700264】；
Step 3 takes the nitrogen-doped graphene quantum dot aqueous solution of 5mL after purification to be aoxidized with 20mL oxide etch agent trioctylphosphine
The phosphorus aqueous solution is mixed, and is transferred to ptfe autoclave, adds the nickel foam cleaned, is carried out at a temperature of 180 DEG C at hydro-thermal
Reason 12 hours, obtains the three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound grown in nickel foam surface in situ
(NiOx-NGQDs/NF)。
Above-mentioned preparation method, the concentration of the described nitrogen-doped graphene quantum dot aqueous solution after purification is 0.5mg/mL
The concentration of the described trioctylphosphine oxide aqueous solution is 0.95mg/mL；Described nickel foam size is 0.5cm x 0.5cm x
1.6mm
Directly take NiOx- NGQDs/NF is electrode, and with NiOx/ NF, NGQDs/NF and a certain amount of business ruthenic oxide of load
(RuO2/ NF) catalyst be control material, in the 1mol/L potassium hydroxide electrolytes of saturation oxygen, test OER electrocatalysis
Energy.
The present invention characterizes prepared NiO by SEMxThe pattern of-NGQDs/NF composites is special
Levy, as shown in Figure 1A, the pure foam nickel cleaned is the smooth 3-D solid structure in surface, passes through oxide etch and N doping stone
After black alkene quantum dot is compound, obtained NiOx- NGQDs/NF compounds still remain the 3-D solid structure (figure of nickel foam
1B), and in its surface etch the hole of a large amount of micron-scales (Fig. 1 C, D), this is beneficial to the ratio surface for improving compound
Product, and promote the output of the mass transfer and product during electro-catalysis.Pass through Fourier-infared spectrum (Fig. 2A), solid fluorescence figure
Compose the sign of (Fig. 2 B), electron spectrum (Fig. 2 C) and X-ray powder diffraction (Fig. 2 D), it was demonstrated that nickel oxide and N doping graphite
Alkene quantum dot has successfully loaded to foam nickel surface.By obtained NiOxAlkali of-NGQDs/NF the composites in oxygen saturation
Its OER electrocatalysis characteristics are tested in property solution, compared with control material, NiOx- NGQDs/NF composite material exhibits go out bigger
Electro-catalysis current density (Fig. 3 A), lower overpotential (10mA/cm2At current density, Fig. 3 B).Meanwhile, test NiOx-
NGQDs/NF composites are to the stability of OER electro-catalysis, before and after the stability experiment process of 20 hours, the composite
Electrocatalysis characteristic is held essentially constant (Fig. 3 C, D), illustrates that the composite has excellent stability.
The advantage of the invention is that：
(1) catalyst surface is handled by simple oxide etch technology, obtains multiple hole surface, lifting catalysis
Agent specific surface area, and then realize the purpose of increase OER catalytic activity.
(2) by synchronous composite reactive conductive compositions (nitrogen-doped graphene quantum dot), the avtive spot of catalyst is increased,
It further enhancing OER performances.
(3) composite structure constructed by is controllable and shows superior OER electrocatalysis characteristics, can substitute noble metal
The use of catalyst.
The present invention utilizes oxide etch from increase specific surface area of catalyst and active site, electric conductivity aspect
Technology formation pore space structure synchronously carries out answering for electrical conductive activities component nitrogen-doped graphene quantum dot to increase specific surface area
Close, largely improve the analysis oxygen electrocatalysis characteristic of catalyst.The preparation method is simple, conveniently, it is inexpensive, what is obtained is compound
Material shows superior electrocatalysis characteristic in alkaline system to oxygen evolution reaction.
Brief description of the drawings
Fig. 1 is the nickel foam scanning electron microscope (SEM) photograph (A) and prepared NiO that are related in the present inventionx- NGQDs/NF ESEM
Scheme (B-D)；
Fig. 2 is the prepared NiO of the present inventionx- NGQDs/NF Fourier-infrared spectrogram (A), solid fluorescence figure (B), electricity
Sub- energy spectrum diagram (C) and X-ray powder diffraction figure (D)；
Fig. 3 is the NiO that the present invention relates tox-NGQDs/NF、NiOx/ NF, NGQDs/NF and RuO2/ NF is urged OER electricity
Change performance test obtain linear sweep voltammetry curve (A), current density be 10mA/cm2Locate the excessively electric of each catalyst of correspondence
Position block diagram (B), NiOx- NGQDs/NF chronoa mperometric plot (C) and NiOx- NGQDs/NF is surveyed before and after test chrono-amperometric
The linear sweep voltammetry curve (D) of examination.
Embodiment
The preparation of the nitrogen-doped graphene quantum dot of embodiment 1.
Nitrogen-doped graphene quantum dot is synthesized using improved microwave method【Referring to：Lv J-J, Zhao J, Fang H,
Jiang L-P, Li L-L, Ma J*, and Zhu J-J*, Incorporating Nitrogen-Doped Graphene
Quantum Dots and Ni3S2Nanosheets：A Synergistic Electrocatalyst with Highly
Enhanced Activity for Overall Water Splitting, Small, 2017,13 (24), 1700264】, including
Following steps：
(1) appropriate remove seed watermelon flesh is taken, smashs to pieces into and is put into after juice in 100mL ptfe autoclaves, in 180 DEG C of temperature
The lower hydro-thermal process of degree 12 hours, by the black carbon gel permeation of acquisition, vacuum drying；
(2) it is placed in after taking carbon gel abrasive made from 0.5g in quartz boat, with 10 DEG C/minute in tube furnace under nitrogen atmosphere
The speed of clock is warming up to 800 DEG C and is pyrolyzed 30 minutes, and products therefrom is carefully mixed with 15mL concentrated nitric acids and the 30mL concentrated sulfuric acids, mixes
Thing is heated to reflux 3 hours (microwave power 400W) in micro-wave oven, is cooled to after room temperature, and brown product is used under condition of ice bath
Sodium hydroxide is adjusted to neutrality.Suspension is obtained by 0.22 μm of micro-pore-film filtration, the dialysis membrane dialysis treatment that molecular weight is 1000
The nitrogen-doped graphene quantum dot of jaundice green fluorescence.
The growth in situ of embodiment 2. is in the preparation of nickel foam surface oxidation nickel and nitrogen-doped graphene quantum dot compound, tool
Body step is as follows：
(1) ethanol, water is respectively adopted and is cleaned by ultrasonic nickel foam (size：0.5cm x 0.5cm) 30 minutes, then put
Dried in 40 DEG C of vacuum drying chambers stand-by；
(2) take 5mL purifying, it is quantitative after the nitrogen-doped graphene quantum dot aqueous solution (0.5mg/mL) and 20mL oxide etch
The agent trioctylphosphine oxide aqueous solution (0.95mg/mL) is mixed, and is transferred to 30mL ptfe autoclaves, adds the foam cleaned
Nickel (size：0.5cm x 0.5cm), hydro-thermal process is carried out at a temperature of 180 DEG C 12 hours, be cooled to after room temperature, product uses two
Secondary water and alcohol flushing are dried in vacuum drying chamber several times and at 50 DEG C, obtain growth in situ in nickel foam surface oxidation nickel and nitrogen
Doped graphene quantum dot compound.
The growth in situ of embodiment 3. is in the sign of nickel foam surface oxidation nickel and nitrogen-doped graphene quantum dot compound, bag
Include：
(1) appearance structure (Fig. 1) of associated materials is characterized using SEM, test result shows resulting
Compound remains the three-dimensional porous structure of nickel foam, and has etched a large amount of micron-sized holes in surface oxidation, is conducive to
Increase specific surface area；
(2) functional group (Fig. 2A), answering obtained by as a result showing contained by Fourier-infrared spectrum (FT-IR) sign material
Condensation material contains-COOH ,-OH etc. and comes from the functional group on nitrogen-doped graphene quantum dot and the Ni-O bases in nickel oxide
Group, the formation of preliminary explanation compound；
(3) Solid fluorescene spectrum characterizes the fluorescent characteristics (Fig. 2 B) of material, and the composite obtained by as a result showing has
Obvious fluorescence signal, further illustrates that nitrogen-doped graphene quantum dot is successfully mixed；
(4) electron spectrum characterizes the element composition (Fig. 2 C) of material, as a result shows that the compound mainly contains Ni, O, C, N
This several element, respectively from nickel oxide and nitrogen-doped graphene quantum dot, it was demonstrated that the formation of compound；
(5) crystal formation feature (Fig. 2 D) of the X-ray powder diffraction spectrogram to characterize material, as a result mainly shows nickel oxide
Characteristic peak corresponding with carbon point, the nickel oxide and nitrogen-doped graphene quantum dot compound crystal formation feature that has of having coincide.
Embodiment 4. only adds trioctylphosphine oxide hydro-thermal process to obtain the growth in situ in nickel foam as control material
Nickel oxide compound (NiOx/ NF), that is, add the 25mL trioctylphosphine oxides aqueous solution (0.95mg/mL) and nickel foam (size：
0.5cm x 0.5cm) carry out 180 DEG C of hydro-thermal process obtain within 12 hours；Only nitrogen-doped graphene quantum dot is added to obtain in nickel foam
Area load graphene quantum dot compound (NGQDs/NF), that is, add 25mL nitrogen-doped graphenes quantum dot (0.1mg/mL) and
Nickel foam (size：0.5cm x 0.5cm x 1.6mm, quality：60mg) 180 DEG C of hydro-thermal process are carried out to obtain for 12 hours.
Electro-catalysis of the growth in situ of embodiment 5. in nickel foam surface oxidation nickel and nitrogen-doped graphene quantum dot compound
Oxygen evolution reaction performance test, mainly includes：
Electrochemistry experiment is carried out on CHI 760E work stations, and electrolyte is that the 1mol/L potassium hydroxide of oxygen saturation is molten
Liquid, using the three-electrode system of standard, wherein platinum electrode is as to electrode, and saturation silver/silver chloride electrode is reference electrode, multiple
Compound electrode or control material electrode are working electrode (area：0.82cm2)。
Test result is as shown in figure 3, the OER electro catalytic activities of composite electrode are better than independent nickel oxide, N doping graphite
Alkene quantum dot and business ruthenic oxide electrode, composite electrode have lower overpotential and Geng Gao electro-catalysis electric current close
Degree, and composite electrode also shows excellent electro-catalysis stability.
Embodiment described above expresses the building process of efficient oxygen evolution reaction catalysts proposed by the invention, its describe compared with
To be specific and detailed, but it can not therefore be defined as the limitation to the scope of the claims of the present invention.It should be pointed out that not departing from this
In invention and appended spirit and scope by the claims, various lithographic technique processing elctro-catalysts or composite reactive component make
The lifting of its electrocatalysis characteristic is all possible.Therefore, the present invention is not only limited to embodiment disclosure of that, application claims
The scope of protection should be determined by the appended claims.
Claims (4)
1. a kind of three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound, it is characterized in that：Described compound be with
Nickel foam is matrix, and a large amount of micron-sized holes have been etched in nickel foam surface oxidation, while the three-dimensional for retaining nickel foam is more
Pore structure, and in foam nickel surface formation nickel oxide and nitrogen-doped graphene quantum dot compound.
2. the preparation method of the three-dimensional porous nickel oxide and nitrogen-doped graphene quantum dot compound described in a kind of claim 1,
It is characterized in that it comprises the following steps：
Step 1. is respectively adopted ethanol, secondary water and is cleaned by ultrasonic nickel foam 30 minutes, is then placed on 40 DEG C of vacuum drying chambers
Middle drying is stand-by；
Step 2. prepares nitrogen-doped graphene quantum dot using improved microwave process for synthesizing, that is, uses biomass watermelon flesh for carbon
Source and nitrogen source, are obtained by the process processing such as hydro-thermal, dialysis, pyrolysis, microwave, purifying, quantitative；
Step 3. takes 5mL purifying, it is quantitative after the nitrogen-doped graphene quantum dot aqueous solution and 20mL oxide etch agent trioctylphosphine oxygen
Change the phosphorus aqueous solution to mix, be transferred to ptfe autoclave, add the nickel foam cleaned, hydro-thermal is carried out at a temperature of 180 DEG C
Processing, obtains the nickel oxide and nitrogen-doped graphene quantum dot compound (NiO grown in nickel foam surface in situx-NGQDs/
NF)。
3. preparation method according to claim 2, it is characterized in that：Described nitrogen-doped graphene quantum dot water after purification
The concentration of solution is that the concentration of the trioctylphosphine oxide aqueous solution described in 0.5mg/mL is 0.95mg/mL；Described nickel foam is big
Small is 0.5cm x 0.5cm x 1.6mm.
4. the three-dimensional porous nickel oxide described in claim 1 is with nitrogen-doped graphene quantum dot compound in electro-catalysis oxygen evolution reaction
The middle application as catalyst.
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