CN107999133A - A kind of preparation and utilization of new HER electrochemical catalysts - Google Patents
A kind of preparation and utilization of new HER electrochemical catalysts Download PDFInfo
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- CN107999133A CN107999133A CN201711233904.9A CN201711233904A CN107999133A CN 107999133 A CN107999133 A CN 107999133A CN 201711233904 A CN201711233904 A CN 201711233904A CN 107999133 A CN107999133 A CN 107999133A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 18
- 238000005286 illumination Methods 0.000 claims abstract description 14
- 239000002078 nanoshell Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000005119 centrifugation Methods 0.000 claims description 26
- 230000001476 alcoholic effect Effects 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000007306 functionalization reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001507 sample dispersion Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 230000002708 enhancing effect Effects 0.000 claims description 5
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 3
- 239000002245 particle Substances 0.000 claims 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 229910017912 NH2OH Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 1
- 229960001790 sodium citrate Drugs 0.000 claims 1
- 239000001509 sodium citrate Substances 0.000 claims 1
- 235000011083 sodium citrates Nutrition 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 description 14
- 229910002696 Ag-Au Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 101150047356 dec-1 gene Proteins 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 208000000747 high pressure neurological syndrome Diseases 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010287 polarization Effects 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- B01J35/396—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a kind of preparation and utilization of new HER electrochemical catalysts, comprise the following steps：The synthesis of S1, Nano silver grain；The synthesis of the golden Porous hollow nanoshell of S2, silver；S3, metallic surface synthesize MOF；S4, the calcining of sample and phosphatization.The preparation and utilization of the new HER electrochemical catalysts, with plasmonic enhancement effects, and combine and also have one layer of FeP outside spherical shell, starting overpotential can further be reduced, therefore comparatively there is more excellent electrochemical catalysis performance and stability, due to material possessed special construction in itself, under conditions of illumination, illumination performance has a greater degree of booster action with respect to other materials, under conditions of potential is 0.5V, the photoelectric current of the Ag AuHPNSs@FeP of synthesis is maximum, in addition, the onset potential of Ag AuHPNSs@FeP is 108mV, Tafel curve slope is 108mVdec‑1, it is minimum with respect to other materials, so that the catalytic efficiency of thus obtained new energy catalyst is improved.
Description
Technical field
The present invention relates to field of new energy technologies, is specially a kind of preparation and utilization of new HER electrochemical catalysts.
Background technology
New energy：Also known as unconventional energy resource.Refer to the various energy forms outside traditional energy.Finger just starts to develop
Or actively study, need the energy promoted, such as solar energy, geothermal energy, wind energy, ocean energy, biomass energy and nuclear fusion energy
Deng.
The energy is that traditional fossil energy gradually uses up and in a short time an important factor for influencing current social development
It is non-renewable, and the exploitation of new energy and application are more in line with development and the needs of modern society, wind energy, Hydrogen Energy in new energy
With solar energy etc. all within the utilization scope of people, during using solar energy, such as during the utilization of illumination
Catalyst plays an important role, and the chemical property of catalyst is poor and stability is not strong, may result in catalyst to energy
The enhancement effect of source conversion reaction is weaker, may result in that the photoelectric current of synthetic material is smaller, directly results in new energy catalyst
Catalytic efficiency is low.
The content of the invention
(1) technical problem solved
In view of the deficiencies of the prior art, the present invention provides a kind of preparation and utilization of new HER electrochemical catalysts, solution
Determine during using solar energy, for example catalyst plays an important role during the utilization of illumination, and catalyst
Chemical property is poor and stability is not strong, it is weaker to may result in the enhancement effect that catalyst reacts energy conversion, will
Cause the photoelectric current of synthetic material smaller, directly result in new energy catalyst catalytic efficiency it is low the problem of.
(2) technical solution
To achieve the above object, the present invention provides following technical solution：
A kind of preparation of new HER electrochemical catalysts, comprises the following steps：
The synthesis of S1, Nano silver grain：
A1, after all glass apparatus to be used are soaked a few minutes with chloroazotic acid, washed away totally with secondary water.
0.125mlAgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2.
A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3mlsodiumcitrate (W:1%) and
2mlVC(0.1M)。
A4, by after gained mixed solution heating 5-10min in above-mentioned steps c1, for several times and disperseed with secondary water centrifuge washing
In deionized water.
The synthesis of the golden Porous hollow nanoshell of S2, silver：
B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted.
B2, be slowly added to 1mlNH2OH (0.1M) and 2mlHAuCl4 (W into the solution after dilution:0.1%), constantly use
Magnetic agitation.
B3, by gained mixed solution condenses in above-mentioned steps b2 and several minutes of the postcoolings that flow back are to room temperature.
B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, makes its reaction rather
Clock.
B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water.
S3, metallic surface synthesize MOF：
C1 will add 10mlPVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated
30min, is then dispersed in alcohol again.
C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10mlMAA (0.015M) alcohol it is molten
Liquid-functionalization, after magnetic agitation 1h, is then sonicated 40min, and it is molten to be then dispersed in alcohol afterwards several times with alcohol centrifuge washing
In liquid.
C3, will be dispersed in the alcoholic solution of 4mlFeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and
Solution is heated into 15min in 70 degree of water-bath, then with alcohol centrifuge washing.
C4, will add 4mlH3btc (2mM) alcohol after alcoholic solution centrifugation of the gained in above-mentioned steps c3 containing metallic
Solution, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing.
After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution.
S4, the calcining of sample and phosphatization：
D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air)
2h is calcined, and is cooled to room temperature.
D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room
Temperature.
Preferably, in the synthesis step of the Nano silver grain in a1 steps, by institute's glass apparatus chloroazotic acid to be used
Immersion 3-5 minutes.
Preferably, gained in step b2 is mixed in b3 steps in the synthesis step of the more aerial empty nanoshells of the silver gold
Solution condenses and the 20-30 minutes postcoolings that flow back are to room temperature；B4 steps in the synthesis step of the more aerial empty nanoshells of silver gold
In, excessive H2O2 (0.1M) 0.2ml is added in solution after cooling into step b3, it is reacted 6-8 minutes.
Preferably, it is described to be synthesized on metallic surface in MOF steps in c2 steps, by the solution after being handled in step c1
Centrifugation adds 10mlMAA (0.015M) alcoholic solution-functionalization after going supernatant, after magnetic agitation 1h, is then sonicated
40min, then with being dispersed in after alcohol centrifuge washing 4-6 times in alcoholic solution.
Preferably, the high-performance HER catalysts with plasmonic effects, it is anti-to HER in the condition of illumination
There should be stronger enhancement effect, it is thus obtained new using development of the design feature to new energy catalyst with reference to effect
The catalytic efficiency of energy catalyst is improved, and is applied in sun transformation of energy and is caused the efficiency of solar energy Transformation Application more
It is high.
(3) beneficial effect
Compared with prior art, the beneficial effects of the invention are as follows：The preparation and utilization of the new HER electrochemical catalysts,
The Ag-AuHPNSs@FeP structures of synthesis are hollow porous nano ball shell, have plasmonic enhancement effects, and combine ball
There is one layer of FeP outside shell, can further reduce starting overpotential, therefore comparatively there is more excellent electrochemical catalysis
Performance and stability, due to material possessed special construction in itself, under conditions of illumination, illumination performance is with respect to other materials
There is a greater degree of booster action, under conditions of potential is -0.5V, the photoelectric current of the Ag-AuHPNSs@FeP of synthesis is maximum,
In addition, the onset potential of Ag-AuHPNSs@FeP is 108mV, Tafel curve slope is 108mV dec-1, with respect to other materials
It is minimum, so that the catalytic efficiency of thus obtained new energy catalyst is improved.
Brief description of the drawings
Fig. 1 is the schematic diagram of photoelectric current difference of the present invention；
Fig. 2 originates superpotential schematic diagram for each material of the present invention；
Fig. 3 is the schematic diagram of Tafel slope of the present invention；
Fig. 4 is the schematic diagram of the TEM for the AgNPs that the present invention synthesizes；
Fig. 5 is the schematic diagram of the TEM for the AuNPs that the present invention synthesizes；
Fig. 6 is the schematic diagram of the TEM for the Ag-AuNPs that the present invention synthesizes；
Fig. 7 is the schematic diagram of the TEM for the Ag-AuHPNSs that the present invention synthesizes；
Fig. 8 is the schematic diagram of the TEM for the Ag@FeP that the present invention synthesizes；
Fig. 9 is the schematic diagram of the TEM for the Au@FeP that the present invention synthesizes；
Figure 10 is the schematic diagram of the TEM for the Ag-Au@FeP that the present invention synthesizes；
Figure 11 is the schematic diagram of the TEM for the Ag-AuHPNSs@FeP that the present invention synthesizes；
Figure 12 is the schematic diagram of electro-chemical test polarization curve of the present invention；
Figure 13 is the schematic diagram of electro-chemical test i-t curves of the present invention；
Figure 14 is the schematic diagram of Tafel curve of the present invention.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment, belongs to the scope of protection of the invention.
As represented in figures 1 through 14, the present invention provides a kind of technical solution：
A kind of preparation and utilization of new HER electrochemical catalysts, comprise the following steps：
The synthesis of S1, Nano silver grain：
A1, after all glass apparatus to be used are soaked 3-5 minutes with chloroazotic acid, washed away totally with secondary water.
0.125mlAgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2.
A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3mlsodiumcitrate (W:1%) and
2mlVC(0.1M)。
A4, by after gained mixed solution heating 5-10min in above-mentioned steps c1, for several times and disperseed with secondary water centrifuge washing
In deionized water.
The synthesis of the golden Porous hollow nanoshell of S2, silver：
B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted.
B2, be slowly added to 1mlNH2OH (0.1M) and 2mlHAuCl4 (W into the solution after dilution:0.1%), constantly use
Magnetic agitation.
B3, by gained mixed solution condenses in above-mentioned steps b2 and the 20-30 minutes postcoolings of number that flow back are to room temperature.
B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, it is reacted 6-8
Minute.
B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water.
S3, metallic surface synthesize MOF：
C1 will add 10mlPVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated
30min, is then dispersed in alcohol again.
C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10mlMAA (0.015M) alcohol it is molten
Liquid-functionalization, after magnetic agitation 1h, is then sonicated 40min, then with being dispersed in alcohol after alcohol centrifuge washing 4-6 times
In solution.
C3, will be dispersed in the alcoholic solution of 4mlFeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and
Solution is heated into 15min in 70 degree of water-bath, then with alcohol centrifuge washing.
C4, will add 4mlH3btc (2mM) alcohol after alcoholic solution centrifugation of the gained in above-mentioned steps c3 containing metallic
Solution, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing.
After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution.
S4, the calcining of sample and phosphatization：
D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air)
2h is calcined, and is cooled to room temperature.
D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room
Temperature, has the high-performance HER catalysts of plasmonic effects, has stronger enhancing to imitate HER reactions in the condition of illumination
Should, using development of the design feature to new energy catalyst with reference to effect, the catalysis of thus obtained new energy catalyst
Efficiency is improved, and is applied to and is caused the more efficient of solar energy Transformation Application in sun transformation of energy.
Embodiment one
A kind of preparation and utilization of new HER electrochemical catalysts, comprise the following steps：
The synthesis of S1, Nano silver grain：
A1, after all glass apparatus to be used are soaked 3 minutes with chloroazotic acid, washed away totally with secondary water.
0.125mlAgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2.
A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3mlsodiumcitrate (W:1%) and
2mlVC(0.1M)。
A4, by after gained mixed solution heating 5min in above-mentioned steps c1, for several times and be dispersed in secondary water centrifuge washing
In deionized water.
The synthesis of the golden Porous hollow nanoshell of S2, silver：
B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted.
B2, be slowly added to 1mlNH2OH (0.1M) and 2mlHAuCl4 (W into the solution after dilution:0.1%), constantly use
Magnetic agitation.
B3, condense gained mixed solution in above-mentioned steps b2 and the number that flows back is cooled to room temperature after twenty minutes.
B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, it is reacted 6 points
Clock.
B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water.
S3, metallic surface synthesize MOF：
C1 will add 10mlPVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated
30min, is then dispersed in alcohol again.
C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10mlMAA (0.015M) alcohol it is molten
Liquid-functionalization, after magnetic agitation 1h, is then sonicated 40min, then molten with alcohol is dispersed in after alcohol centrifuge washing 4 times
In liquid.
C3, will be dispersed in the alcoholic solution of 4mlFeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and
Solution is heated into 15min in 70 degree of water-bath, then with alcohol centrifuge washing.
C4, will add 4mlH3btc (2mM) alcohol after alcoholic solution centrifugation of the gained in above-mentioned steps c3 containing metallic
Solution, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing.
After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution.
S4, the calcining of sample and phosphatization：
D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air)
2h is calcined, and is cooled to room temperature.
D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room
Temperature, has the high-performance HER catalysts of plasmonic effects, has stronger enhancing to imitate HER reactions in the condition of illumination
Should, using development of the design feature to new energy catalyst with reference to effect, the catalysis of thus obtained new energy catalyst
Efficiency is improved, and is applied to and is caused the more efficient of solar energy Transformation Application in sun transformation of energy.
Embodiment two
A kind of preparation and utilization of new HER electrochemical catalysts, comprise the following steps：
The synthesis of S1, Nano silver grain：
A1, after all glass apparatus to be used are soaked 4 minutes with chloroazotic acid, washed away totally with secondary water.
0.125mlAgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2.
A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3mlsodiumcitrate (W:1%) and
2mlVC(0.1M)。
A4, by after gained mixed solution heating 7.5min in above-mentioned steps c1, for several times and disperseed with secondary water centrifuge washing
In deionized water.
The synthesis of the golden Porous hollow nanoshell of S2, silver：
B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted.
B2, be slowly added to 1mlNH2OH (0.1M) and 2mlHAuCl4 (W into the solution after dilution:0.1%), constantly use
Magnetic agitation.
B3, by gained mixed solution condenses in above-mentioned steps b2 and the 25 minutes postcoolings of number that flow back are to room temperature.
B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, it is reacted 7 points
Clock.
B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water.
S3, metallic surface synthesize MOF：
C1 will add 10mlPVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated
30min, is then dispersed in alcohol again.
C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10mlMAA (0.015M) alcohol it is molten
Liquid-functionalization, after magnetic agitation 1h, is then sonicated 40min, then molten with alcohol is dispersed in after alcohol centrifuge washing 5 times
In liquid.
C3, will be dispersed in the alcoholic solution of 4mlFeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and
Solution is heated into 15min in 70 degree of water-bath, then with alcohol centrifuge washing.
C4, will add 4mlH3btc (2mM) alcohol after alcoholic solution centrifugation of the gained in above-mentioned steps c3 containing metallic
Solution, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing.
After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution.
S4, the calcining of sample and phosphatization：
D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air)
2h is calcined, and is cooled to room temperature.
D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room
Temperature, has the high-performance HER catalysts of plasmonic effects, has stronger enhancing to imitate HER reactions in the condition of illumination
Should, using development of the design feature to new energy catalyst with reference to effect, the catalysis of thus obtained new energy catalyst
Efficiency is improved, and is applied to and is caused the more efficient of solar energy Transformation Application in sun transformation of energy.
Embodiment three
A kind of preparation and utilization of new HER electrochemical catalysts, comprise the following steps：
The synthesis of S1, Nano silver grain：
A1, by all glass apparatus to be used with chloroazotic acid soak after five minutes, washed away totally with secondary water.
0.125mlAgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2.
A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3mlsodiumcitrate (W:1%) and
2mlVC(0.1M)。
A4, by after gained mixed solution heating 10min in above-mentioned steps c1, for several times and be dispersed in secondary water centrifuge washing
In deionized water.
The synthesis of the golden Porous hollow nanoshell of S2, silver：
B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted.
B2, be slowly added to 1mlNH2OH (0.1M) and 2mlHAuCl4 (W into the solution after dilution:0.1%), constantly use
Magnetic agitation.
B3, by gained mixed solution condenses in above-mentioned steps b2 and the 30 minutes postcoolings of number that flow back are to room temperature.
B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, it is reacted 8 points
Clock.
B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water.
S3, metallic surface synthesize MOF：
C1 will add 10mlPVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated
30min, is then dispersed in alcohol again.
C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10mlMAA (0.015M) alcohol it is molten
Liquid-functionalization, after magnetic agitation 1h, is then sonicated 40min, then molten with alcohol is dispersed in after alcohol centrifuge washing 6 times
In liquid.
C3, will be dispersed in the alcoholic solution of 4mlFeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and
Solution is heated into 15min in 70 degree of water-bath, then with alcohol centrifuge washing.
C4, will add 4mlH3btc (2mM) alcohol after alcoholic solution centrifugation of the gained in above-mentioned steps c3 containing metallic
Solution, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing.
After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution.
S4, the calcining of sample and phosphatization：
D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air)
2h is calcined, and is cooled to room temperature.
D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room
Temperature, has the high-performance HER catalysts of plasmonic effects, has stronger enhancing to imitate HER reactions in the condition of illumination
Should, using development of the design feature to new energy catalyst with reference to effect, the catalysis of thus obtained new energy catalyst
Efficiency is improved, and is applied to and is caused the more efficient of solar energy Transformation Application in sun transformation of energy.
It can to sum up obtain, the preparation and utilization of the new HER electrochemical catalysts, the Ag-Au HPNSs@FeP structures of synthesis
For hollow porous nano ball shell, there is plasmonic enhancement effects, and combine and also have one layer of FeP outside spherical shell, can be further
Starting overpotential is reduced, therefore comparatively there is more excellent electrochemical catalysis performance and stability, due to material in itself
Possessed special construction, under conditions of illumination, illumination performance has a greater degree of booster action with respect to other materials, in electricity
Under conditions of gesture is -0.5V, the photoelectric current of the Ag-AuHPNSs@FeP of synthesis is maximum, in addition, the starting of Ag-AuHPNSs@FeP
Potential is 108mV, and Tafel curve slope is 108mVdec-1, is minimum with respect to other materials, so that thus obtaining
The catalytic efficiency of new energy catalyst be improved.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of changes, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (5)
- A kind of 1. preparation of new HER electrochemical catalysts, it is characterised in that：Comprise the following steps：The synthesis of S1, Nano silver grain：A1, after all glass apparatus to be used are soaked a few minutes with chloroazotic acid, washed away totally with secondary water；0.125ml AgNO3 (0.2M), be dispersed in the deionized water of 50ml and use magnetic agitation by a2；A3, by after resulting solution is heated to boiling in above-mentioned steps a2, add 3ml sodiumcitrate (W:And 2ml 1%) VC(0.1M)；A4, by after gained mixed solution heating 5-10min in above-mentioned steps c1, for several times and be dispersed in secondary water centrifuge washing In ionized water；The synthesis of the golden Porous hollow nanoshell of S2, silver：B1, take in above-mentioned steps S1 gained Nano silver grain 50ml and add 50ml deionized waters and diluted；B2, be slowly added to 1ml NH2OH (0.1M) and 2ml HAuCl4 (W into the solution after dilution:0.1%) magnetic, is constantly used Power stirs；B3, by gained mixed solution condenses in above-mentioned steps b2 and several minutes of the postcoolings that flow back are to room temperature；B4, add excessive H2O2 (0.1M) 0.2ml into above-mentioned steps b3 in solution after cooling, it is reacted a few minutes；B5, by resulting solution centrifuge washing in above-mentioned steps b4 for several times afterwards disperse in deionized water；S3, metallic surface synthesize MOF：C1 will add 10ml PVP (55000,20g/L) in above-mentioned steps S2 after the centrifugation of gained metallic, be ultrasonically treated 30min, is then dispersed in alcohol again；C2, will be handled in above-mentioned steps c1 after solution centrifugation go after supernatant to add 10ml MAA (0.015M) alcoholic solution- Functionalization, after magnetic agitation 1h, is then sonicated 40min, is then dispersed in alcoholic solution afterwards several times with alcohol centrifuge washing In；C3, will be dispersed in the alcoholic solution of 4ml FeCl3-6H2O (2mM) after the metallic centrifugation after functionalization, and will be molten Liquid heats 15min in 70 degree of water-bath, then with alcohol centrifuge washing；C4, will in above-mentioned steps c3 gained containing metallic alcoholic solution centrifugation after add 4ml H3btc (2mM) alcohol it is molten Liquid, and 30min is heated in 70 degree of water-bath, it is then centrifuged for washing；After c5, the above-mentioned c3 and c4 steps 8 time of repetition, by gained sample dispersion in alcoholic solution；S4, the calcining of sample and phosphatization：D1, by above-mentioned steps S3 gained sample dried in 60 degree of baking oven after, under conditions of 500 degree (in air) calcining 2h, and be cooled to room temperature；D2, by above-mentioned steps d1 gained sample placed in Ar and under conditions of 450 degree, phosphatization 2h postcoolings to room temperature.
- A kind of 2. preparation of new HER electrochemical catalysts according to claim 1, it is characterised in that：The silver nanoparticle In the synthesis step of particle in a1 steps, institute's glass apparatus to be used chloroazotic acid is soaked 3-5 minutes.
- A kind of 3. preparation of new HER electrochemical catalysts according to claim 1, it is characterised in that：The silver gold is more In the synthesis step of aerial sky nanoshell in b3 steps, after gained mixed solution in step b2 is condensed and flowed back 20-30 minutes It is cooled to room temperature；In the synthesis step of the more aerial empty nanoshells of silver gold in b4 steps, the solution after cooling into step b3 It is middle to add excessive H2O2 (0.1M) 0.2ml, it is reacted 6-8 minutes.
- A kind of 4. preparation of new HER electrochemical catalysts according to claim 1, it is characterised in that：It is described in metal In particle surface synthesis MOF steps in c2 steps, the solution centrifugation after being handled in step c1 adds 10ml after going supernatant MAA (0.015M) alcoholic solution-functionalization, after magnetic agitation 1h, is then sonicated 40min, then with alcohol centrifuge washing It is dispersed in after 4-6 times in alcoholic solution.
- 5. according to a kind of utilization of new HER electrochemical catalysts of claim 1-4 any one of them, it is characterised in that：Institute The high-performance HER catalysts with plasmonic effects are stated, have stronger enhancing to imitate HER reactions in the condition of illumination Should, using development of the design feature to new energy catalyst with reference to effect, the catalysis of thus obtained new energy catalyst Efficiency is improved, and is applied to and is caused the more efficient of solar energy Transformation Application in sun transformation of energy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105241939A (en) * | 2015-09-16 | 2016-01-13 | 山东理工大学 | Preparation method for immunosensor based on gold/silver core-shell magnetic graphene adsorption cadmium ion and application |
| CN105688958A (en) * | 2016-01-15 | 2016-06-22 | 复旦大学 | Polyhedron cobalt phosphide/graphite carbon hybrid material and preparing method and application thereof |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105241939A (en) * | 2015-09-16 | 2016-01-13 | 山东理工大学 | Preparation method for immunosensor based on gold/silver core-shell magnetic graphene adsorption cadmium ion and application |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105688958A (en) * | 2016-01-15 | 2016-06-22 | 复旦大学 | Polyhedron cobalt phosphide/graphite carbon hybrid material and preparing method and application thereof |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
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