CN108704663A - A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon - Google Patents
A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon Download PDFInfo
- Publication number
- CN108704663A CN108704663A CN201810525914.8A CN201810525914A CN108704663A CN 108704663 A CN108704663 A CN 108704663A CN 201810525914 A CN201810525914 A CN 201810525914A CN 108704663 A CN108704663 A CN 108704663A
- Authority
- CN
- China
- Prior art keywords
- preparation
- ethyl alcohol
- solution
- btc
- absolute ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000003756 stirring Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 33
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 238000010792 warming Methods 0.000 claims abstract description 15
- 239000013147 Cu3(BTC)2 Substances 0.000 claims abstract description 14
- 239000013049 sediment Substances 0.000 claims abstract description 13
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 55
- 235000019441 ethanol Nutrition 0.000 claims description 30
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
- 230000005611 electricity Effects 0.000 claims description 12
- 229910009112 xH2O Inorganic materials 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 239000003643 water by type Substances 0.000 description 20
- 125000005909 ethyl alcohol group Chemical group 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method 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
- 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—
-
- B01J35/60—
Abstract
The invention discloses a kind of preparation methods of the nano combined electrocatalysis material of bimetallic carbon, include the following steps：1) mantoquita is dissolved in water, stirs to blue-tinted transparent, obtains solution A；2) trimesic acid is dissolved in absolute ethyl alcohol and the in the mixed solvent of DMF, stirs to get solution B；3) by solution A and solution B ultrasound 1-3h after evenly mixing, sediment washing is placed on dry 1-3h in 40-80 DEG C of baking oven, obtains Cu3(BTC)2Presoma；4) by Cu3(BTC)2It is dispersed in deionized water and the in the mixed solvent of absolute ethyl alcohol, RuCl is added3·xH2After O is stirred to react 4-24h, centrifugation obtains sediment, it is used dry the bimetallic MOFs materials containing Cu and Ru after absolute ethyl alcohol washing；5) MOFs materials are placed in tube furnace, are warming up to 400-700 DEG C in an inert atmosphere and keep the temperature 1-5h, be cooled to room temperature, obtain the nano combined electrocatalysis material CuRu/C of the bimetallic carbon containing Cu and Ru.Preparation method of the present invention is simple, at low cost, catalytic performance is excellent.
Description
Technical field
The invention belongs to technical field of material chemistry, more particularly, to a kind of nano combined electro-catalysis of bimetallic carbon containing Cu and Ru
The preparation method of material.
Background technology
With the rapid development of social economy, energy and environment become the problem of people's growing interest, solar energy and wind energy
Etc. regenerative resources consumption proportion shared in the consumption of human society total energy also step up.But due to this kind of renewable
There are certain pauses and fluctuation for electric energy during conversion and use for the energy, so, rechargeable battery, electrochemical capacitor
The technologies such as the electrochemical energy storages such as device, electrolytic cell and fuel cell and conversion, in terms of realizing efficiently with sustainable using energy source
Very crucial effect will be played.Although their operation principle is different, these electrochemical appliances are all by similar key
What functional unit was constituted, and the functional material being used in these components electrochemical properties (such as redox and catalysis live
Property) by the overall performance of determination device.Therefore, preparing the functional material of excellent electrochemical performance, to have become electrochemical field important
Research direction.
Hydrogen has the advantages that high-energy density and production environmental protection are achievable, it is considered to be the ideal of sustainable energy economy
Energy carrier.Water decomposition production hydrogen is the chief component of contemporary clean energy technology, however due to current potential in water splitting processes
Excessive, its practical application is very limited.So water dissociation technology efficiently, inexpensive will play the application of hydrogen energy source
Vital effect.During hydrogen is produced in water decomposition, suitable catalyst use can effectively reduce reaction activity, from
And accelerate reaction process and hydrogen generation efficiency.Currently, most widely used catalyst is based primarily upon Pt based nano-materials, but the earth's crust
The middle limited own cost of content is higher, thus find the alternative catalysis material of low cost be present material research hot spot it
One.
Metal-organic framework (MOFs) material has type numerous as a kind of novel porous hybrid inorganic-organic materials
It is more, it is vdiverse in function, structure is adjustable the features such as.It is similar with inorganic material, the MOFs containing redox active metal centres
With certain electro-chemical activity.MOFs has the metallic site of organic molecule coordination and is easy the pore structure adjusted, this is also
The optimization of its performance provides architecture basics.Now, there are many relevant document reports, by regulating and controlling metal and having
Machine component constructs compound MOFs materials, and MOFs is used successfully as to the electrode material of rechargeable battery and electrochemical capacitor, is used for
The efficient elctro-catalyst of fuel cell, or even for the electrolyte of electrochemical appliance, but there are still chemically by most of MOFs
The unstable disadvantage with electric conductivity difference of matter.Recently, it is available metallic compound and carbonization by MOFs material thermal conversions
The research of object catalysis material has caused widely to pay attention to, research shows that functional material derived from these MOF not only remains originally
The good characteristic of material, and chemical property can it is more stable, electric conductivity is more preferable, usually have very excellent catalytic
Can, there is highly important potentiality to be exploited in electrochemical field.
Currently, what the basic research of electro-catalysis production hydrogen (HER) mainly carried out in acid condition, it is anti-to be primarily due to it
Answer approach relatively easy, this also causes direction research application to have some limitations.In recent years, document report is gradually begun with
The material for adulterating Ru is applied to HER electro-catalysis testing researches by road.Compared with Pt, Ru prices have certain advantage, price
About 1st/15th of Pt.In addition, Ru has bond strength similar with hydrogen, still, it is catalyzed as HER now concerning Ru
The report of agent is still less.It can also optimize material catalysis using the atom doped base metal base carbon composite of extraneous metal to live
Property.The content for being doped into the metal ions such as Cu not only and can further decreasing Ru can also further promote material to reduce the cost
Expect performance.
Invention content
For overcome the deficiencies in the prior art, the present invention provide it is a kind of it is with good HER electrocatalysis characteristics, containing Cu and
The preparation method of the nano combined electrocatalysis material of bimetallic carbon of Ru.
The technical solution adopted by the present invention to solve the technical problems is：A kind of nano combined electrocatalysis material of bimetallic carbon
Preparation method comprising following steps：
1) mantoquita is dissolved in deionized water, stirring to blue-tinted transparent, it is 0.01-0.03 mol/ to obtain copper ion concentration
The solution A of mL；
2) trimesic acid is dissolved in absolute ethyl alcohol and the in the mixed solvent of DMF, stirs to water white transparency, obtains solution B,
Wherein ethyl alcohol：DMF=1:1-3；
3) it by solution A and solution B ultrasound 1-3h after evenly mixing, is collected by centrifugation to obtain the sediment of blue, by sediment
It is placed on dry 1-3h in 40-80 DEG C of baking oven using absolute ethyl alcohol washing, obtains Cu3(BTC)2Presoma；
4) Cu that will be obtained in step 3)3(BTC)2It is dispersed in deionized water and the in the mixed solvent of absolute ethyl alcohol, mixing is molten
The volume of agent is 10-30ml, and RuCl is added3·xH2After O is stirred to react 4-24h, centrifugation obtains navy blue sediment, will precipitate
Object is placed on dry 1-3h in 50-70 DEG C of baking oven using absolute ethyl alcohol washing, obtains the bimetallic MOFs materials containing Cu and Ru
Material；
5) the MOFs materials obtained in step 4) are placed in tube furnace, in an inert atmosphere with the liter of 1-20 DEG C/min
Reactant is warming up to 400-700 DEG C and keeps the temperature 1-5h by warm rate, is cooled to room temperature, and is obtained multiple containing Cu and Ru bimetallic carbon nanometers
Close electrocatalysis material CuRu/C.
Further, the mantoquita in the step 1) is copper acetate or copper sulphate or copper chloride or two or three arbitrary
Combination.
Further, the amount ratio of the substance of mantoquita and trimesic acid is 0.5-5 in the step 3):1.
Further, copper ion concentration is 0.02mol/mL in the step 1).
Further, H in the step 4)3A concentration of 0.013mol/mL of BTC.
Further, water in the step 2)：Ethyl alcohol：DMF=1:1:2.
Further, Cu in the step 4)3(BTC)2And RuCl2·xH2The amount ratio of the substance of O is 1-10:1；
RuCl2·xH2A concentration of 0.04mol/ml of O.
Further, the volume ratio of water and absolute ethyl alcohol is 1 in the step 4):The volume of 1-2, mixed solvent is
20ml。
Further, inert atmosphere is nitrogen or argon gas in the step 5).
Further, reactant is warming up to 400-600 DEG C and keeps the temperature in the step 5).
The preparation method of the present invention is further to find the bimetallic that preparation method is simple, at low cost, catalytic performance is excellent
Carbon nano-composite material is goal in research, synthesizes MOFs material Cs u first3(BTC)2, and carry out ion as presoma and Ru
Bimetallic MOFs materials are prepared in exchange, are finally carried out high temperature pyrolysis to bimetallic MOFs materials at 400-700 DEG C, are obtained stone
Carbon nano-composite material derived from the high bimetallic organic framework materials of blackization degree.The material has bigger serface, structure
Rule, uniform doping, the feature being evenly distributed is a kind of electrocatalysis material haveing excellent performance.
The beneficial effects of the invention are as follows：The bimetallic MOFs materials containing Cu and Ru are synthesized using ion-exchange, are passed through after
High-temperature calcination is crossed, the nano combined electricity containing Cu and Ru bimetallic carbon with bigger serface, tactical rule, uniform doping is obtained
Catalysis material is a kind of electrocatalysis material haveing excellent performance.
Description of the drawings
(a) (b) is the scanning electron microscopic picture of the CuRu-BTC prepared by the embodiment of the present invention 1 in Fig. 1；(c) (d) is implemented
The scanning electron microscopic picture of the nano combined electrocatalysis material containing Cu and Ru bimetallic carbon after being heat-treated in example 1.
It is the nano combined electrocatalysis material containing Cu and Ru bimetallic carbon prepared by the embodiment of the present invention 1,2,3,4 in Fig. 2
XRD diagram.
Fig. 3 is the EDS collection of illustrative plates of the nano combined electrocatalysis material containing Cu and Ru bimetallic carbon after being heat-treated in embodiment 1.
Fig. 4 is the corresponding LSV curves of sample difference rate of charge.
Fig. 5 is the corresponding Tafel slope curves of sample difference rate of charge.
Specific implementation mode
In order to make those skilled in the art be better understood from the present invention program, below in conjunction in the embodiment of the present invention
Attached drawing carries out clear, complete description to the technical solution in inventive embodiments, it is clear that described embodiment is only this
A part of the embodiment of invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without making creative work, should all belong to the scope of protection of the invention.
Embodiment 1
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, obtain copper ion ([Cu2+]) a concentration of 0.02mol/mL solution A；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.013mol/mL；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.571mL3·xH2O is stirred for 24 hours；
(d) product is centrifuged to obtain navy blue sediment, absolute ethyl alcohol washing is used in combination three times, it is then dry at 60 DEG C
2h；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 10 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 3h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u6Ru/C。
As shown in figure 3, sample composition mainly contains tetra- kinds of Cu, Ru, C, O, wherein C, O comes from ligand trimesic acid, Cu,
Ru then comes from metal salt.It can be seen that four kinds of elements are evenly distributed in the sample by Fig. 3 (a), by Fig. 3 (b) it can be seen that sample
Cu6Practical Cu, Ru ratio is about 9 in Ru/C：1.Result above can be very good to prove the synthesis of final material CuRu/C.
The composite material has preferable HER performances, in the KOH electrolyte of 1mol/L, current density 10mA/cm-2
When, overpotential only has 20-80mV.
Embodiment 2
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, get Dao [Cu2+]The solution A of=0.02mol/mL；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.013mol/mL；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 1.748mL3·xH2O is stirred for 24 hours；
(d) product is centrifuged to obtain navy blue sediment, absolute ethyl alcohol washing is used in combination three times, it is then dry at 60 DEG C
2h；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 10 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 3h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u2Ru/C。
Embodiment 3
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, get Dao [Cu2+]The solution A of=0.02mol/mL；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, stirring is until form the solution of water white transparency, get Dao [BTC3-]=0.013mol/mL
Solution B；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.857mL3·xH2O is stirred for 24 hours；
(d) product is centrifuged to obtain navy blue sediment, absolute ethyl alcohol washing is used in combination three times, it is then dry at 60 DEG C
2h；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under argon atmosphere with 10 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 3h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u4Ru/C。
Embodiment 4
(1)Cu3(BTC)2The preparation of presoma：
(a) by 0.4mol Cu (CH3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, get Dao [Cu2+]The solution A of=0.02mol/mL；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, stirring is until form the solution of water white transparency, get Dao [BTC3-]=0.013mol/mL
Solution B；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O is stirred for 24 hours；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 10 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 3h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C。
In fig. 2, we can see that the XRD spectrum and principal character peak of CuxRu/C with Cu crystal analogue spectrums
(04-0836) is consistent.And its characteristic diffraction peak also coincide with Cu crystal characteristic diffraction maximums, i.e. (111), (200), (220),
Show that the crystallinity of Cu in sample CuxRu/C is preferable.There is no more sharp C diffraction maximums in diffracting spectrum, this shows to be obtained
Carbon be amorphous carbon, Ru diffraction maximums also not sharp, show that Ru is distributed in support C well in diffracting spectrum, this with
The result that EDS is shown is consistent.
The increase with Ru ratios in rate of charge, sample electro catalytic activity first increases and then decreases are can be seen that in conjunction with Fig. 4,5.
In Cu：Ru=6：Sample has best catalytic activity when 1, at this time sample Cu6When electric current is 10mA, overpotential only has Ru/C
22mV, Tafel slope only have 49mV*dec-1, which extremely connects with best electrolysis aquatic products hydrogen catalyst Pt/C performances at present
Closely, and overpotential ratio Pt/C also wants low (when electric current is 10mA, overpotential 31mV).This illustrates the prepared sample of this experiment
With extremely excellent electrocatalysis characteristic, this depends on height of Cu, Ru bimetallic in material entirety point in the material
The features such as scattered and bimetallic synergistic effect, material bigger serface, high porosity, provides for this excellent electrocatalysis characteristic
Architecture basics.
Embodiment 5
(1)Cu3(BTC)2The preparation of presoma：
(a) by the CuSO of 0.4mol4·5H2O is dissolved in 20mL deionized waters, and stirring is until form the molten of blue-tinted transparent
Liquid, get Dao [Cu2+]The solution A of=0.02mol/mL；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, stirring is until form the solution of water white transparency, get Dao [BTC3-]=0.013mol/mL
Solution B；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O stirs 4h；
(d) product is centrifuged to obtain navy blue sediment, absolute ethyl alcohol washing is used in combination three times, it is then dry at 60 DEG C
2h；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 1 DEG C/
The rate of min is warming up to 400 DEG C, keeps the temperature 1h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-1。
Embodiment 6
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, get Dao [Cu2+]The solution A of=0.02mol/mL；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, stirring is until form the solution of water white transparency, get Dao [BTC3-]=0.013mol/mL
Solution B；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 10mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O stirs 14h；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 20 DEG C/
The rate of min is warming up to 600 DEG C, keeps the temperature 5h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-2。
Embodiment 7
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.6mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, obtain copper ion concentration be 0.03mol/mL solution A；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.013mol/mL；
(c) solution A is added in solution B, ultrasound 3h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 1h at 80 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 20mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O stirs 14h；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 1.5h at 70 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 15 DEG C/
The rate of min is warming up to 400 DEG C, keeps the temperature 5h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-3。
Embodiment 8
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, obtain copper ion concentration be 0.02mol/mL solution A；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 60mL, volume ratio 1:2, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.013mol/mL；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 20mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O stirs 10h；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2.5h at 55 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 18 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 5h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-4。
Embodiment 9
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.2mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, obtain copper ion concentration be 0.01mol/mL solution A；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 80mL, volume ratio 1:2, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.01mol/mL；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 20mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O is stirred for 24 hours；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 20 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 3h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-5。
Embodiment 10
(1)Cu3(BTC)2The preparation of presoma：
(a) by the Cu (CH of 0.4mol3COO)2·H2O is dissolved in 20mL deionized waters, and stirring is until form blue-tinted transparent
Solution, obtain copper ion concentration be 0.02mol/mL solution A；
(b) by the trimesic acid (H of 0.8mol3BTC it) is added in absolute ethyl alcohol and DMF, wherein absolute ethyl alcohol and DMF
Total volume be 80mL, volume ratio 1:3, solution of the stirring up to forming water white transparency obtains H3BTC's is a concentration of
The solution B of 0.01mol/mL；
(c) solution A is added in solution B, ultrasound 2h after stirring evenly；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(2) preparation of bimetal composite MOFs materials：
(a) the 100mg Cu that will be obtained3(BTC)2It is scattered in 10mL deionized waters and 20mL absolute ethyl alcohols, is added
The RuCl of a concentration of 0.04mol/ml of 0.428mL3·xH2O stirs 14h；
(d) product is centrifuged and is washed three times with ethyl alcohol, then the dry 2h at 60 DEG C；
(3) preparation of CuRu/C materials：
Product-bimetal composite MOFs materials that (2) obtain are placed in tube furnace, under nitrogen atmosphere with 10 DEG C/
The rate of min is warming up to 500 DEG C, keeps the temperature 5h, is then cooled to room temperature, obtains the nano combined electricity containing Cu and Ru bimetallic carbon and urge
Change material C u8Ru/C-6。
Above-mentioned specific implementation mode is used for illustrating the present invention, rather than limits the invention, the present invention's
In spirit and scope of the claims, to any modifications and changes that the present invention makes, the protection model of the present invention is both fallen within
It encloses.
Claims (10)
1. a kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon, it is characterised in that include the following steps：
1) mantoquita is dissolved in deionized water, stirring to blue-tinted transparent, it is the molten of 0.01-0.03mol/mL to obtain copper ion concentration
Liquid A；
2) trimesic acid is dissolved in absolute ethyl alcohol and the in the mixed solvent of DMF, stirs to water white transparency, obtains solution B, wherein
Ethyl alcohol：DMF=1:1-3；
3) it by solution A and solution B ultrasound 1-3h after evenly mixing, is collected by centrifugation to obtain the sediment of blue, sediment is used
Absolute ethyl alcohol washing is placed on dry 1-3h in 40-80 DEG C of baking oven, obtains Cu3(BTC)2Presoma；
4) Cu that will be obtained in step 3)3(BTC)2It is dispersed in deionized water and the in the mixed solvent of absolute ethyl alcohol, mixed solvent
Volume is 10-30ml, and RuCl is added3·xH2After O is stirred to react 4-24h, centrifugation obtains navy blue sediment, and sediment is made
Dry 1-3h in the baking oven for be placed on 50-70 DEG C is washed with absolute ethyl alcohol, obtains the bimetallic MOFs materials containing Cu and Ru；
5) the MOFs materials obtained in step 4) are placed in tube furnace, in an inert atmosphere with the heating rate of 1-20 DEG C/min
Reactant is warming up to 400-700 DEG C and keeps the temperature 1-5h, is cooled to room temperature, the nano combined electricity containing Cu and Ru bimetallic carbon is obtained and urges
Change material C uRu/C.
2. preparation method according to claim 1, it is characterised in that：Mantoquita in the step 1) is copper acetate or sulfuric acid
Copper or copper chloride or arbitrary two or three of combination.
3. preparation method according to claim 1, it is characterised in that：The object of mantoquita and trimesic acid in the step 3)
The amount ratio of matter is 0.5-5:1.
4. preparation method according to claim 1, it is characterised in that：Copper ion concentration is 0.02mol/ in the step 1)
mL。
5. preparation method according to claim 1, it is characterised in that：H in the step 4)3BTC's is a concentration of
0.013mol/mL。
6. preparation method according to claim 1, it is characterised in that：Water in the step 2)：Ethyl alcohol：DMF=1:1:2.
7. preparation method according to claim 1, it is characterised in that：Cu in the step 4)3(BTC)2And RuCl2·xH2O
Substance amount ratio be 1-10:1；RuCl2·xH2A concentration of 0.04mol/ml of O.
8. preparation method according to claim 1, it is characterised in that：The volume ratio of water and absolute ethyl alcohol in the step 4)
It is 1:The volume of 1-2, mixed solvent are 20ml.
9. preparation method according to claim 1, it is characterised in that：Inert atmosphere is nitrogen or argon in the step 5)
Gas.
10. preparation method according to claim 1, it is characterised in that：Reactant is warming up to 400-600 in the step 5)
DEG C and keep the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810525914.8A CN108704663A (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810525914.8A CN108704663A (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108704663A true CN108704663A (en) | 2018-10-26 |
Family
ID=63870724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810525914.8A Pending CN108704663A (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108704663A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109570527A (en) * | 2019-01-11 | 2019-04-05 | 盐城工学院 | A kind of preparation method of confinement type nano zero valence iron nickel composite |
| CN111137874A (en) * | 2020-01-10 | 2020-05-12 | 南昌航空大学 | Method for preparing composite wave-absorbing material by taking HKUST-1 as template |
| CN111701569A (en) * | 2020-05-29 | 2020-09-25 | 北京建筑大学 | Bimetal organic framework derived porous carbon and preparation method and application thereof |
| CN113185399A (en) * | 2021-04-30 | 2021-07-30 | 北京化工大学 | Metal copper complex and application thereof in electrochemistry CO2Application in reduction |
| CN113471457A (en) * | 2021-07-13 | 2021-10-01 | 福建师范大学 | Preparation and application of cationic MOFs derivative catalyst |
| CN115260513A (en) * | 2022-07-29 | 2022-11-01 | 广东石油化工学院 | Hierarchical porous MOFs material containing CuRu bimetal and preparation method and application thereof |
| CN115814812A (en) * | 2022-09-02 | 2023-03-21 | 江苏大学 | Preparation method and application of bimetallic MOFs derivative with superoxide dismutase activity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN104269566A (en) * | 2014-09-22 | 2015-01-07 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon nano sheet composite material |
-
2018
- 2018-05-29 CN CN201810525914.8A patent/CN108704663A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN104269566A (en) * | 2014-09-22 | 2015-01-07 | 南开大学 | Preparation method and application of nitrogen-doped porous carbon nano sheet composite material |
| CN104269566B (en) * | 2014-09-22 | 2016-11-30 | 南开大学 | A kind of preparation method and application of N doping porous carbon nanosheet composite material |
Non-Patent Citations (2)
| Title |
|---|
| HONG ZHANG ET AL.,: "MOF-derived nanohybrids for electrocatalysis and energy storage: current status and perspectives", 《 CHEM. COMMUN.》 * |
| PRADIP PACHFULE ET AL.,: "From Ru nanoparticle-encapsulated metal–organic frameworks to highly catalytically active Cu/Ru nanoparticle-embedded porous carbon", 《J. MATER. CHEM. A》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109570527A (en) * | 2019-01-11 | 2019-04-05 | 盐城工学院 | A kind of preparation method of confinement type nano zero valence iron nickel composite |
| CN109570527B (en) * | 2019-01-11 | 2022-06-10 | 盐城工学院 | Preparation method of limited-domain nano zero-valent iron-nickel compound |
| CN111137874A (en) * | 2020-01-10 | 2020-05-12 | 南昌航空大学 | Method for preparing composite wave-absorbing material by taking HKUST-1 as template |
| CN111137874B (en) * | 2020-01-10 | 2023-03-31 | 南昌航空大学 | Method for preparing composite wave-absorbing material by taking HKUST-1 as template |
| CN111701569A (en) * | 2020-05-29 | 2020-09-25 | 北京建筑大学 | Bimetal organic framework derived porous carbon and preparation method and application thereof |
| CN111701569B (en) * | 2020-05-29 | 2023-04-28 | 北京建筑大学 | Bimetal organic framework derived porous carbon and preparation method and application thereof |
| CN113185399A (en) * | 2021-04-30 | 2021-07-30 | 北京化工大学 | Metal copper complex and application thereof in electrochemistry CO2Application in reduction |
| CN113471457A (en) * | 2021-07-13 | 2021-10-01 | 福建师范大学 | Preparation and application of cationic MOFs derivative catalyst |
| CN115260513A (en) * | 2022-07-29 | 2022-11-01 | 广东石油化工学院 | Hierarchical porous MOFs material containing CuRu bimetal and preparation method and application thereof |
| CN115814812A (en) * | 2022-09-02 | 2023-03-21 | 江苏大学 | Preparation method and application of bimetallic MOFs derivative with superoxide dismutase activity |
| CN115814812B (en) * | 2022-09-02 | 2024-03-19 | 江苏大学 | Preparation method and application of bi-metal MOFs derivative with superoxide dismutase activity |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN108704663A (en) | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon | |
| CN109252180B (en) | Ternary MOF nanosheet array material, preparation method and application thereof | |
| Shang et al. | In situ growth of NixSy controlled by surface treatment of nickel foam as efficient electrocatalyst for oxygen evolution reaction | |
| CN108716008A (en) | Three-dimensional ferronickel layered double-hydroxide array and its room temperature preparation method and application | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN109524678A (en) | A kind of analysis oxygen ferrocobalt-cobalt ferrite/nitrogen-doped nanometer carbon pipe composite catalyst and its preparation method and application | |
| CN107604375A (en) | Difunctional VPO catalysts of the porous carbon complex of nitrogen cobalt codope and its preparation method and application | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN105618060A (en) | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof | |
| CN110075853B (en) | Electrocatalytic fully-decomposed water CoZn-LDHs-ZIF @ C composite structure material, and preparation method and application thereof | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN107051568A (en) | One kind analysis oxygen Fe two cobaltous selenide@N CT composite catalysts of doping and its preparation method and application | |
| CN105731437B (en) | A kind of exotic atom doped graphene and the preparation method and application thereof | |
| CN110474057A (en) | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon | |
| JP7434372B2 (en) | Method for producing nickel-iron catalyst material, use in oxygen evolution reaction, method for producing hydrogen and/or oxygen by water electrolysis, and method for producing liquid solar fuel | |
| CN108716007A (en) | The method for improving hydroxide electrocatalytic hydrogen evolution reactivity worth by Lacking oxygen engineering | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN113105645B (en) | Preparation method, product and application of nickel-based metal organic framework compound | |
| CN110904468B (en) | Cerium-doped tungsten phosphide submicron sphere composite material and preparation method and application thereof | |
| CN110624573A (en) | Nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and preparation method thereof | |
| CN111193038A (en) | Nickel cobalt iron hydroxide coated nickel cobaltate flexible electrode material and preparation and application thereof | |
| CN110400939A (en) | A kind of preparation method of biomass nitrating porous carbon oxygen reduction catalyst | |
| CN103316679A (en) | Preparation method of ordered mesoporous non-noble metal-nitrogen-graphitized carbon material | |
| CN113355682B (en) | Iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181026 |
|
| RJ01 | Rejection of invention patent application after publication |