CN107088432A - A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application - Google Patents
A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application Download PDFInfo
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- 239000002060 nanoflake Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000000034 method Methods 0.000 claims abstract description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 6
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims abstract description 6
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims abstract description 6
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims abstract description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005642 Oleic acid Substances 0.000 claims abstract description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- -1 Acyl acetone nickel Chemical compound 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015335 Ni2In Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a kind of Ru doping Ni2P plate-like nano flakes and preparation method thereof and the application as bifunctional electrocatalyst in evolving hydrogen reaction (HER) and oxygen evolution reaction (OER).The preparation method is by nickel formate/nickel acetylacetonate, ruthenium trichloride/acetylacetone,2,4-pentanedione ruthenium, positive tri octyl phosphine, after lauryl amine and oleic acid ultrasonic mixing, temperature programming is incubated after 60 120min to 280 300 DEG C of reactions, room temperature is naturally cooling to, is centrifuged, washs obtained Ru doping Ni after drying2P plate-like nano flakes.The preparation method passes through one pot process two dimension Ru doping Ni at ambient pressure2P plate-like nano flakes, technique is simple, repeatability is strong.Two-dimentional Ru doping Ni of the present invention2P plate-like nano flakes show excellent electrocatalysis characteristic, and it can be applied to HER and OER simultaneously as bifunctional electrocatalyst, be had broad application prospects in field of renewable energy such as electrolysis waters.
Description
Technical field
The present invention relates to a kind of nano material and its preparation and application, more particularly to a kind of two-dimentional Ru doping Ni2P plate-likes are received
Rice thin slice and preparation method thereof and the application as bifunctional electrocatalyst in evolving hydrogen reaction (HER) and oxygen evolution reaction (OER).
Background technology
Global energy crisis and environmental pollution cause scientists in the urgent need to find green, cleaning, it is reproducible
New energy system replaces traditional fossil fuel system.In future source of energy application system, electro-catalysis hydrolysis prepare hydrogen and
Oxygen is considered as a kind of source of preferable renewable and clean energy resource, thus is aroused widespread concern.
Electrolysis water reaction includes two half-reactions：Cathode hydrogen evolution reacts and Oxygen anodic evolution reaction.At present, scientists are generally acknowledged
Best catalytic hydrogen evolution and the catalyst of oxygen evolution reaction be made up of respectively Pt and ruthenium/iridium oxide, but due to the storage of its earth
Amount is few, and the reason such as expensive limits the extensive development that electrolysis water is originated as a kind of green regenerative energy sources.In addition,
Some good HER catalyst but show general or even poor electro catalytic activity to catalysis OER, and vice versa.Accordingly, it is capable to same
Shi Cuihua HER and OER high activity, the development significance of low-cost dual-function elctro-catalyst are great.
Due to the unique and excellent electrocatalysis characteristic of structure, transition metal phosphide receives extensive pass in recent years
Note.Ni2P is mainly made up of the Ni elements of earth rich content, shown excellent as a kind of important transition metal phosphide
Electro-catalysis HER performances.Theoretical calculation also indicates that Ni2P (001) crystal face has the Δ G of appropriatenessH, accordingly with best
HER performances, are most to have one of HER catalyst of application prospect.However, Ni2P is used for reduction reaction, and analysis oxygen is limited in one's ability.Root
According to the literature, doping can generally change the microcosmic electronic structure of catalyst, show the electrocatalysis characteristic of optimization.
The content of the invention
It is an object of the invention to provide a kind of two-dimentional Ru doping Ni2The preparation method of P plate-like nano flakes.It is described to prepare
Method uses non-aqueous system synthetic method simple and easy to apply, and having obtained two-dimentional Ru by simple one-pot synthesis at ambient pressure adulterates
Ni2P plate-like nano flakes, methods described technique is simple, repeatability is strong.
Another object of the present invention is to provide a kind of two-dimentional Ru doping Ni prepared by the above method2P plate-likes
Nano flake.
Another object of the present invention also resides in the above-mentioned two-dimentional Ru doping Ni of offer2P plate-likes nano flake is used as difunctional electricity
Application of the catalyst in HER and OER.
The purpose of the present invention is achieved through the following technical solutions：
A kind of two-dimentional Ru doping Ni2The preparation method of P plate-like nano flakes, it is characterised in that methods described includes following
Step：
(1) by nickel source (nickel formate or nickel acetylacetonate), ruthenium source (ruthenium trichloride or acetylacetone,2,4-pentanedione ruthenium), (positive three is pungent for phosphorus source
Base phosphine, TOP), reducing agent (lauryl amine, DDA) and solvent/protective agent (oleic acid, OA) ultrasound mix, then temperature programming is to 280-
Room temperature is naturally cooling to after 300 DEG C of reactions, insulation 60-120min；
(2) reaction product is centrifuged, washs obtained Ru doping Ni after drying2P plate-like nano flakes.
In methods described, the ratio of the amount of the material that feeds intake in nickel source and ruthenium source is 3~5: 1.
In methods described, mole/volume ratio of nickel source and positive tri octyl phosphine is 0.15~0.5 (mmol/mL).
In methods described, step (1) programmed rate is preferably 7 DEG C of min-1, the reaction time is preferably 60min.
In methods described, step (2) uses ethanol and normal heptane centrifuge washing, finally dries under vacuum.
Two-dimentional Ru doping Ni of the present invention2The preparation method of P plate-like nano flakes uses non-water body simple and easy to apply
It is method, using the two-dimentional Ru doping Ni described in one pot process simple and easy to apply2P plate-like nano flakes.The inventive method is two
Tie up Ru doping Ni2In the preparation of P plate-like nano flakes, the presoma of nickel source used, ruthenium source and phosphorus source is respectively nickel formate/second
Acyl acetone nickel, ruthenium trichloride/acetylacetone,2,4-pentanedione ruthenium and positive tri octyl phosphine, reducing agent is lauryl amine, and solvent/protective agent is oleic acid；Just
Tri octyl phosphine is phosphorus source and surface capping reagents, influences size and the plate-like concave surface of nanometer sheet；And reducing agent lauryl amine is excessive
.The preparation method condition is simple, and repeatability is strong, and operation possibility is high, it is easy to accomplish.
The invention further relates to one kind two dimension Ru doping Ni as made from above-mentioned preparation method2P plate-like nano flakes.
The two-dimentional Ru doping Ni2P plate-likes nano flake is the Ni that hexagonal phase Ru adulterates2The ultra-thin chip architecture of P two dimension plate-likes.
Wherein, plane lattice spacing is 0.33nm, correspondence hexagonal phase Ni2Between P (JCPDS 65-9706) (001) crystal face, plane lattice
Away from for 0.22nm, correspondence Ni2(the two has similar (100) crystal face of P (111) crystal face or hexagonal phase Ru (JCPDS 65-1863)
Lattice fringe spacing).
The two-dimentional Ru doping Ni2The diameter of P plate-like nano flakes is about 20.5~42.5nm.
The invention further relates to above-mentioned two-dimentional Ru doping Ni2P plate-likes nano flake as bifunctional electrocatalyst in HER and
Application in OER.
Using evolving hydrogen reaction and oxygen evolution reaction as probe reaction, the electrocatalysis characteristic of gained nano material has been investigated.Using
Two dimension Ru doping Ni made from preparation method of the present invention2P plate-likes nano flake binary phosphide Ni corresponding with Ni, P2P compares table
Reveal more excellent electrocatalysis characteristic.For evolving hydrogen reaction (HER), two-dimentional Ru doping Ni of the present invention2P plate-like nano flakes
Show to be substantially better than binary Ni2The initial potential (- 35mV) and Tafel slope of P nanometer sheets and close commercialization 20%Pt/C
(34mV dec-1)；For oxygen evolution reaction (OER), two-dimentional Ru doping Ni of the present invention2P plate-like nano flakes are shown substantially
Better than binary Ni2P nanometer sheets and 20%Pt/C and close commercialization IrO2Initial potential (1.54V), voltage be 1.6V when electricity
Current density (3.61mAcm-2) and current density be 10mA cm-2When overpotential η10(0.49V).This is mainly due to catalyst
Special plate-like nano flake structure has the faster electron transfer rate of bigger specific surface area；In addition, plate-like nanometer sheet surface
Expose substantial amounts of high activity Ni2P (001) crystal face, promotes the lifting of electrocatalysis characteristic.
Beneficial effects of the present invention：The preparation method of the present invention two dimension by simple one pot process at ambient pressure
Ru doping Ni2P plate-like nano flakes, technique is simple, repeatability is strong.Two-dimentional Ru doping Ni of the present invention2P plate-likes nanometer
Thin slice has the advantages that simple cheap, preparation, excellent performance, had a wide range of application, and is expected to large-scale application in electrolysis water body
System, the source as green, clean reproducible energy.
Brief description of the drawings
Fig. 1 is two dimension Ru doping Ni made from the embodiment of the present invention 12The EDS figures of P plate-like nano flakes.
Fig. 2 is two dimension Ru doping Ni made from the embodiment of the present invention 12The XRD of P plate-like nano flakes.
Fig. 3 is two dimension Ru doping Ni made from the embodiment of the present invention 12The TEM figures of P plate-like nano flakes.
Fig. 4 is two dimension Ru doping Ni made from the embodiment of the present invention 12The element mapping figures of P plate-like nano flakes.
Fig. 5 is two dimension Ru doping Ni made from the embodiment of the present invention 12The HRTEM figures of P plate-like nano flakes.
Fig. 6 (A) is two dimension Ru doping Ni made from the embodiment of the present invention 12The line in P plate-likes nano flake front (card) is swept
Figure；Fig. 6 (B) is two dimension Ru doping Ni made from the embodiment of the present invention 12The linear sweep graph of P plate-like nano flakes reverse side (the disk back side).
Fig. 7 is two dimension Ru doping Ni made from embodiment 22The TEM figures of P plate-like nano flakes.
Fig. 8 is two dimension Ru doping Ni made from embodiment 32The TEM figures of P plate-like nano flakes.
Fig. 9 is binary Ni prepared by the embodiment of the present invention 42P EDS figures.
Figure 10 is binary Ni prepared by the embodiment of the present invention 42P XRD.
Figure 11 is binary Ni prepared by the embodiment of the present invention 42P TEM figures.
Figure 12 (A) is Ru doping Ni2P(Ru-dopedNi2P)、Ni2The HER polarization curves of P and 20%Pt/C catalyst；
Figure 12 (B) is Ru doping Ni2P、Ni2The HER Tafel slope figures of P and 20%Pt/C catalyst.
Figure 13 (A) is Ru doping Ni2P、Ni2P、IrO2With the OER polarization curves of 20%Pt/C catalyst；Figure 13 (B) is
Ru doping Ni2P、Ni2P、IrO2With 20%Pt/C catalyst current density be 10mA cm-2OER overpotential figure and 1.6V
(vs.RHE) OER current density figures when.
Figure 14 schemes for the TEM of comparative example method synthetic product.
Embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment, but are necessary
Point out that following examples are served only for the description to the content of the invention, do not constitute limiting the scope of the invention.
The two dimension of embodiment 1 Ru doping Ni2The preparation of P plate-like nano flakes
At room temperature, in 250mL three-neck flasks that are clean, drying, 0.22g Ni (COOH) are sequentially added2And 0.10g
RuCl3Ultrasonic disperse formation homogeneous solution after solid, 5mL TOP, 1.5mL OA and 3mL DDA, by above-mentioned solution with 7 DEG C of min-1
Heating rate be heated to 300 DEG C, be incubated 60min, naturally cool to room temperature, finally with ethanol and normal heptane centrifuge washing, point
From obtaining two-dimentional Ru doping Ni after drying2P plate-like nano flakes.
Test is swept to obtained two-dimentional Ru doping Ni using EDS, XRD, TEM, element mapping, HRTEM and line2P plate-likes
Nano flake carries out the sign (such as Fig. 1~6) of component and structure.In Fig. 1 O peak from absorption in the organic of nano-material surface
The carbon that capping reagents and air, C and Cu come from load nano material supports copper mesh, and remaining is tri- kinds of elements of Ru, Ni, P
Peak, Ni/Ru atoms number ratio is close to 16: 5.Two dimension Ru doping Ni in Fig. 22The diffraction maximum of P plate-like nano flakes is mainly corresponded to
Hexagonal phase Ni2P (JCPDS, 65-9706), Ru peak is not obvious, and this is probably but the EDS elementary analyses because Ru content is less
Ru presence is demonstrated with Element area profile (Fig. 6 (A) and (B)), illustrates that the sample that experiment is obtained is hexagonal phase Ru doping
Hexagonal phase Ni2P.TEM figures from Fig. 3 are it can be seen that nano material is very thin plate-like nanometer sheet, and diameter is about 20.5-
42.5nm.The linear sweep graph of element mapping figures and nano flake positive and negative from Fig. 4,6 (A), 6 (B) can be with it is further seen that receive
Rice piece be the semi-transparent structure of plate-like, rather than the transition metal phosphide of document report (table 1 below) hollow structure；And Ru, Ni, P
Element is evenly distributed in whole nanometer sheet.Compared to hollow nano flake, semi-transparent plate-like nano flake connectivity is more preferable,
There are faster electro transfer and transmission rate, the electrocatalysis characteristic of optimization may be shown.Fig. 5 is Ru doping Ni2P nano flakes
HRTEM figures, we can see that nano flake clearly lattice fringe from figure, wherein, the spacing of lattice of plane is
0.33nm, correspondence hexagonal phase Ni2P (JCPDS 65-9706) (001) crystal face, the spacing of lattice of plane is 0.22nm, correspondence
Ni2(the two has between similar lattice fringe (100) crystal face of P (111) crystal face or hexagonal phase Ru (JCPDS 65-1863)
Away from).At the same time, it has been found that nano flake center dish area and fringe region all expose substantial amounts of active Ni2P(001)
Crystal face, the electro catalytic activity that may have caused.
The two dimension of embodiment 2 Ru doping Ni2The preparation of P plate-like nano flakes
At room temperature, in 250mL three-neck flasks that are clean, drying, 0.36g Ni (COOH) are sequentially added2And 0.10g
RuCl3Ultrasonic disperse formation homogeneous solution after solid, 5mL TOP, 1.5mL OA and 3mL DDA, by above-mentioned solution with 7 DEG C of min-1
Heating rate be heated to 300 DEG C, be incubated 60min, naturally cool to room temperature, finally with ethanol and normal heptane centrifuge washing, point
From obtaining two-dimentional Ru doping Ni after drying2P plate-like nano flakes.The TEM of gained nano flake is as shown in Figure 7.
The two dimension of embodiment 3 Ru doping Ni2The preparation of P plate-like nano flakes
At room temperature, in 250mL three-neck flasks that are clean, drying, 0.22g Ni (COOH) are sequentially added2With 0.20g Ru
(acac)2Ultrasonic disperse formation homogeneous solution after solid, 5mL TOP, 1.5mL OA and 3mL DDA, by above-mentioned solution with 7 DEG C
min-1Heating rate be heated to 280 DEG C, be incubated 120min, naturally cool to room temperature, finally washed with ethanol and normal heptane centrifugation
Wash, separate, two-dimentional Ru doping Ni is obtained after drying2P plate-like nano flakes.The TEM of gained nano flake is as shown in Figure 8.
The binary Ni of embodiment 42The preparation of P nanometer sheets
Binary Ni2The preparation of P nanometer sheets and the Ru doping Ni of embodiment 12The preparation method of P nano flakes is similar, difference
It is in no addition RuCl3As Ru sources, by this preparation method, binary Ni is obtained2P nanometer sheets.
To the binary Ni of synthesis2P nanometer sheets carry out EDS (Fig. 9), TEM (Figure 10) and XRD (Figure 11) and characterized, it was demonstrated that experiment
Hexagonal phase Ni is obtained2P nanometer sheets (non-disk-like structure).
The two dimension of embodiment 5 Ru doping Ni2Application of the P nano flakes as bifunctional electrocatalyst in HER and OER
Two-dimentional Ru doping Ni2The method of testing that P nano flakes are catalyzed HER and OER as elctro-catalyst is as follows：
Test the preparation of electrode：Weigh 2.0mg Ru doping Ni2P nano flakes, are dissolved in 0.25mL ethanol and 0.75mL water
Middle ultrasound is into homogeneous mixture solotion, and the concentration of solution is 2.0mg mL-1.The 10 above-mentioned catalyst solutions of μ L are taken, are added dropwise dry
On net glass-carbon electrode (diameter 3mm), after being air-dried, then 5 μ L naphthols are added dropwise, electrochemistry HER tests are can be used to after drying.
For OER tests, method for making sample is similar with HER, and difference is：20 μ L catalyst solutions are added dropwise in clean rotating circular disk
Electrode (5mm), other operations are identical.
Using Ni2P, commercialization IrO2(AlfaAesar) and 20%Pt/C (AlfaAesar) catalyst is prepared in the same way
Test electrode.
For HER tests, first in N2The 0.5M H of saturation2SO4Solution in carry out cyclic voltammetry, scanning range-
0.8~0.2V (vs.AgCl) carries out polarization curve test again after it is stable, and 0~-0.9V of scanning range (vs.AgCl) sweeps speed
5mV s-1.For OER reactions, first in O2Carry out cyclic voltammetry in the 0.1M KOH of saturation solution, scanning range 0~
1V(vs.AgCl).Then the same test for carrying out polarization curve, 0~1V of scanning range (vs.AgCl) sweeps fast 5mV s-1。
Two-dimentional Ru doping Ni of the present invention2P nano flake electro-catalysis HER the performance test results are as shown in figure 12, from
Figure 12 (A) is it can be found that Ru doping Ni2P nano flakes show close with 20%Pt/C but are substantially better than Ni2P initial potential
And current density.In order to further study its catalytic kinetics, we calculate the Tafel slope of catalyst, such as Figure 12 (B)
It is shown, Ru doping Ni2Tafel slope (the 34mV dec of P nano flakes-1) and 20%Pt/C (32mV dec-1) close, it is better than
Ni2P(53mV dec-1) and the transition metal phosphide (table 1) reported recently.
The catalytic performance of the different liberation of hydrogen catalyst of table 1. compares
In addition, OER performance tests are carried out to catalyst, and as a result as shown in Figure 13 (A), Ru doping Ni2Of P nano flakes
The close commercialization IrO of beginning current potential2And it is substantially better than Ni2P and 20%Pt/C.According to the literature, OER is 10mA in current density
cm-2When corresponding overpotential η10Can as catalyst activity criterion, the difference is smaller, shows catalytic activity
It is higher, it can be seen that two dimension Ru doping Ni from Figure 13 (B)2The η of P nano flakes10For 0.49V, better than Ni2P (0.69V) and
20%Pt/C (0.63V), close to IrO2(0.40V).At the same time, two-dimentional Ru doping Ni2P nano flakes are under 1.6V voltage
Show to be better than Ni2P and 20%Pt/C current density.
These test results illustrate Ru doping Ni2P nano flakes show excellent electro-catalysis HER and OER bi-functional,
This can be attributed to：(1) catalyst exposes substantial amounts of high activity Ni2P (001) crystal face, result in excellent electro-catalysis HER
Energy；(2) the special disk-shaped flakes structure of catalyst has bigger specific surface area and faster electron transfer rate to be conducive to catalysis
The lifting of agent electrocatalysis characteristic；(3) Ru doping improves binary phosphide Ni2P electric conductivity and electrocatalysis characteristic.
In summary, Ru doping Ni2P nano flakes show excellent electro-catalysis HER and OER bi-functional, in electrolysis
There is potential application prospect in the fields such as water hydrogen manufacturing, fuel cell.
Comparative example
At room temperature, in 250mL three-neck flasks that are clean, drying, 0.22g Ni (COOH) are sequentially added2And 0.10g
RuCl3Solid, 1mL TOP, 4mL octadecylene (in order to which metal front bulk concentration is constant, instead of the TOP contents of reduction), 1.5mL
Ultrasonic disperse formation homogeneous solution after OA and 3mL DDA, by above-mentioned solution with 7 DEG C of min-1Heating rate be heated to 300 DEG C,
60min is incubated, room temperature is naturally cooled to, finally with ethanol and normal heptane centrifuge washing, separation, product nano is obtained after drying
It is brilliant.The nanocrystalline TEM of gained is as shown in figure 14, without described plate-like nanometer chip architecture.
Claims (9)
1. a kind of two-dimentional Ru doping Ni2The preparation method of P plate-like nano flakes, it is characterised in that methods described includes following step
Suddenly：
(1) by nickel formate or nickel acetylacetonate, ruthenium trichloride or acetylacetone,2,4-pentanedione ruthenium, positive tri octyl phosphine, lauryl amine and oleic acid are ultrasonic
Mix, then temperature programming is incubated after 60-120min to 280-300 DEG C of reaction, is naturally cooling to room temperature；
(2) reaction product is centrifuged, washs the Ru doping Ni for being made described after drying2P plate-like nano flakes.
2. a kind of two-dimentional Ru doping Ni according to claim 12The preparation method of P plate-like nano flakes, it is characterised in that
In methods described, the amount ratio of nickel formate or nickel acetylacetonate and ruthenium trichloride or the material of acetylacetone,2,4-pentanedione ruthenium is 3~5: 1.
3. a kind of two-dimentional Ru doping Ni according to claim 12The preparation method of P plate-like nano flakes, it is characterised in that
In methods described, mole/volume ratio of nickel formate or nickel acetylacetonate and positive tri octyl phosphine is 0.15~0.5mmol/mL.
4. a kind of two-dimentional Ru doping Ni according to claim 12The preparation method of P plate-like nano flakes, it is characterised in that
In methods described, step (1) programmed rate is 7 DEG C of min-1, the reaction time is 60min.
5. a kind of two-dimentional Ru doping Ni according to claim 12The preparation method of P plate-like nano flakes, it is characterised in that
In methods described, step (2) uses ethanol and normal heptane centrifuge washing, finally dries under vacuum.
6. the two dimension Ru doping Ni according to made from Claims 1 to 5 any described method2P plate-like nano flakes.
7. two-dimentional Ru doping Ni according to claim 62P plate-like nano flakes, it is characterised in that described two-dimentional Ru mixes
Miscellaneous Ni2P plate-likes nano flake is disk-like structure, and a diameter of 20.5-42.5nm of nano flake.
8. two-dimentional Ru doping Ni according to claim 62P plate-like nano flakes, it is characterised in that described two-dimentional Ru mixes
Miscellaneous Ni2P plate-likes nano flake is the hexagonal phase Ni that hexagonal phase Ru adulterates2P two dimension plate-like nano flakes.
9. the two-dimentional Ru doping Ni described in claim 62P plate-like nano flakes are as bifunctional electrocatalyst in HER and OER
Application.
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