CN110065932B - Lithium insertion type selenium compound, and preparation method and application thereof - Google Patents
Lithium insertion type selenium compound, and preparation method and application thereof Download PDFInfo
- Publication number
- CN110065932B CN110065932B CN201910405725.1A CN201910405725A CN110065932B CN 110065932 B CN110065932 B CN 110065932B CN 201910405725 A CN201910405725 A CN 201910405725A CN 110065932 B CN110065932 B CN 110065932B
- Authority
- CN
- China
- Prior art keywords
- selenium compound
- compound
- lithium insertion
- irse
- vacuum
- 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.)
- Active
Links
- 229940065287 selenium compound Drugs 0.000 title claims abstract description 64
- 150000003343 selenium compounds Chemical class 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000003780 insertion Methods 0.000 title claims abstract description 34
- 230000037431 insertion Effects 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- UUVABROKEMJIHC-UHFFFAOYSA-N bis(selanylidene)iridium Chemical compound [Ir](=[Se])=[Se] UUVABROKEMJIHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910052711 selenium Inorganic materials 0.000 abstract description 3
- 239000011669 selenium Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011943 nanocatalyst Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JXTNYTBZEWFKNR-UHFFFAOYSA-L dilithium;selenate Chemical compound [Li+].[Li+].[O-][Se]([O-])(=O)=O JXTNYTBZEWFKNR-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a preparation method of a lithium insertion type selenium compound, which comprises the following steps: mixing a selenium compound and an organic lithium compound in an organic solvent, and heating and reacting in a protective atmosphere to obtain a lithium insertion type selenium compound; the selenium compound is a selenium compound of platinum group elements. Compared with the prior art, the lithium insertion type selenium compound is prepared by lithium insertion, the preparation method is simple, the obtained product has high porosity, large specific surface area and selenium vacancy, and the lithium insertion type selenium compound has high activity and high stability in an electrolytic water reaction by utilizing the composite effect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a lithium insertion type selenium compound, and a preparation method and application thereof.
Background
With the enhancement of environmental awareness and the deepening of the knowledge of limited resources, in order to reduce the dependence on non-renewable resources such as petrochemical energy, the search and development of a clean, cheap, convenient and effective energy supply mode has become a first-time task of the energy industry.
Hydrogen, a green fuel, can be simply generated by electrochemical or photochemical water splitting, providing a solution for establishing a sustainable and environmentally friendly energy system. In recent years, development of various low-pollution battery technologies is underway, and particularly, new energy technologies such as a renewable fuel cell, a rechargeable reusable metal-air battery, and electrolytic water are attracting attention. These new energy technologies are based on electrochemical catalytic processes, which require catalysts to reduce the energy consumption of the reaction process. Electrocatalytic water separation includes Hydrogen Evolution (HER) and Oxygen Evolution (OER) reactions, which generally require large overpotentials in the cell due to non-ideal thermodynamics and kinetics of both half-reactions.
Currently, platinum metal oxide and iridium/ruthenium oxide are the benchmark electrocatalysts for HER and OER, respectively. However, the practical use of these individual catalysts in integrated electrolyzers is often hampered by mismatch of operating conditions. In addition, different equipment and processes are required to manufacture the individual catalysts, which increases cost and time. To address these problems, it is necessary to develop bifunctional electrocatalysts for HER and OER in the same electrolyte.
Through research and development, a series of non-noble metal catalysts with low cost and stable performance, such as transition metal sulfides, selenides, phosphides, oxides and hydroxides thereof, appear, but the performance of the non-noble metal catalysts is far different from that of noble metal catalysts, and the non-noble metal catalysts need high loading capacity. Moreover, most of them are only suitable for use in alkaline electrolyzers, although rarely found to be effective under acidic or neutral conditions.
Compared with alkaline electrolyte, the acid electrolyte combined with a Proton Exchange Membrane (PEM) has the advantages of high ionic conductivity, less side reactions, low cost, effective inhibition of gas crossover and the like. A challenge faced in current PEM water splitting is that OER catalysts suffer from corrosion or poor activity in acidic media. In addition, the neutral electrolyte has environmental friendliness and biocompatibility, and can be used for biological upgrading conversion and low-cost direct seawater separation. Unfortunately, few catalysts perform well in neutral media under ambient electrocatalytic conditions. In this case, the dual-function electrocatalyst at three pH's is more and more demanding for overall water splitting, accommodating diverse applications in an adjustable way, but still represents a significant challenge.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a lithium insertion type selenium compound with bifunctional electrocatalyst effect, and a preparation method and an application thereof.
The invention provides a preparation method of a lithium insertion type selenium compound, which comprises the following steps:
mixing a selenium compound and an organic lithium compound in an organic solvent, and heating and reacting in a protective atmosphere to obtain a lithium insertion type selenium compound; the selenium compound is a platinum group element selenium compound.
Preferably, the mass-volume ratio of the selenium compound to the organic lithium compound is (60-100) mg:1ml.
Preferably, the selenium compound is selected from iridium diselenide; the organolithium compound is selected from n-butyllithium.
Preferably, the temperature of the heating reaction is 60-80 ℃; the heating reaction time is 1-5 h.
Preferably, the selenium compound is prepared according to the following method: selenium powder and platinum group metal powder are mixed and calcined in vacuum to obtain the selenium compound.
Preferably, the temperature of the vacuum calcination is 950-1150 ℃; the vacuum calcination time is 25-40 h; vacuum degree of vacuum calcination is 10 -4 ～10 -6 torr。
Preferably, the vacuum calcination comprises a first vacuum calcination and a second vacuum calcination; after the first vacuum calcination, cooling to room temperature, and then carrying out second vacuum calcination.
The invention also provides the prepared lithium insertion type selenium compound.
The invention also provides application of the prepared lithium insertion type selenium compound as a catalyst for electrocatalytic decomposition of water.
Preferably, the solution has a pH of 0 to 14 when water is decomposed by electrocatalysis.
The invention provides a preparation method of a lithium insertion type selenium compound, which comprises the following steps: mixing a selenium compound and an organic lithium compound in an organic solvent, and heating and reacting in a protective atmosphere to obtain a lithium insertion type selenium compound; the selenium compound is a selenium compound of platinum group elements. Compared with the prior art, the lithium insertion type selenium compound is prepared by lithium insertion, the preparation method is simple, the obtained product has high porosity, large specific surface area and selenium vacancy, and the lithium insertion type selenium compound has high activity and high stability in an electrolytic water reaction by utilizing the composite effect.
Experiments show that the lithium insertion type selenium compound prepared by the invention can be used as a high-efficiency bifunctional electrocatalyst for HER and OER with a wide pH value range. In particular for OER, li-IrSe 2 At pH =0 and 7, at 10mA cm -2 The overpotential of (A) is only 180mV and 222mV; furthermore, when Li-IrSe is used 2 Integrated as both positive and negative catalysts into water-splitting cells at pH =0, 7 and 14, at 10mA cm -2 At all pH values, the cell voltage did not exceed 1.50V. Notably, li-IrSe 2 The performance of electrolyzed water at pH =0 was unprecedented, expressed as 10mA cm -2 When the battery voltage is only 1.44V and the battery operates for 24h, the current degradation is not obvious, and the stability is good.
Drawings
FIG. 1a shows the black bulk IrSe obtained in example 1 of the present invention 2 Scanning electron microscope images of;
FIG. 1b shows the black bulk IrSe obtained in example 1 of the present invention 2 Transmission electron microscopy images of;
FIG. 1c shows Li-IrSe obtained in example 1 of the present invention 2 Scanning electron microscope images of;
FIG. 1d shows Li-IrSe obtained in example 1 of the present invention 2 Transmission electron microscopy images of;
FIG. 2 shows the black IrSe bulk obtained in example 1 of the present invention 2 With Li-IrSe 2 X-ray diffraction patterns of (a);
FIG. 3a shows the black bulk IrSe obtained in example 1 of the present invention 2 Voltammetric plots of electrocatalytic hydrogen evolution reactions;
FIG. 3b shows Li-IrSe obtained in example 1 of the present invention 2 Voltammograms of electrocatalytic hydrogen evolution reactions;
FIG. 4a shows the black bulk IrSe obtained in example 1 of the present invention 2 Voltammetric plots of electrocatalytic oxygen production reactions;
FIG. 4b shows Li-IrSe obtained in example 1 of the present invention 2 Voltammetric plots of electrocatalytic oxygen production reactions;
FIG. 5 shows Li-IrSe obtained in example 1 of the present invention 2 Voltammetric curves of the electrolyzed water reaction;
FIG. 6 shows Li-IrSe obtained in example 1 of the present invention 2 Stability profile of electrolyzed water reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a lithium insertion type selenium compound, which comprises the following steps: mixing a selenium compound and an organic lithium compound in an organic solvent, and heating and reacting in a protective atmosphere to obtain a lithium insertion type selenium compound; the selenium compound is a selenium compound of platinum group elements.
In the present invention, the sources of all raw materials are not particularly limited, and the raw materials may be commercially available or self-made.
The selenium compound is a selenium compound of platinum group elements, and more preferably iridium diselenide; the preferred particle size of the selenium compound is 400-600 nm; the selenium compound is preferably prepared according to the following steps: selenium powder and platinum group metal powder are mixed and calcined in vacuum to obtain the selenium compound. The molar ratio of the selenium powder to the platinum group metal powder is preferably 2:1; mixing selenium powder and platinum group metal powder, and preferably grinding; the grinding time is preferably 40-60 min, more preferably 45-55 min, and still more preferably 50min; after grinding, vacuum calcination is carried out; the temperature of the vacuum calcination is preferably 950-1150 ℃, and more preferably 1000 ℃; the time of the vacuum calcination is preferably 25 to 40 hours, and more preferably 30 to 35 hours; the vacuum degree of the vacuum calcination is preferably 10 -4 ～10 -6 torr, more preferably10 -5 torr; in the present invention, the vacuum calcination is preferably performed in two steps, including a first vacuum calcination and a second vacuum calcination, and more preferably, after the first vacuum calcination is finished, the vacuum calcination is naturally cooled to room temperature, and then the second vacuum calcination is performed; preferably, after the first vacuum calcination is finished, the mixture is naturally cooled to room temperature, reactants are shaken, and then the second vacuum calcination is carried out; the temperature of the first vacuum calcination is preferably 950-1150 ℃, and more preferably 1000 ℃; the time of the first vacuum calcination is preferably 10 to 20 hours, more preferably 13 to 18 hours, and still more preferably 15 hours; the heating rate of the first vacuum calcination is preferably 1-10 ℃/min, more preferably 2-8 ℃/min, still more preferably 4-6 ℃/min, and most preferably 5 ℃/min; the temperature of the second vacuum calcination is preferably 950-1150 ℃, and more preferably 1000 ℃; the time of the second vacuum calcination is preferably 10 to 20 hours, more preferably 13 to 18 hours, and still more preferably 15 hours; the heating rate of the second vacuum calcination is preferably 1 to 10 ℃/min, more preferably 2 to 8 ℃/min, still more preferably 4 to 6 ℃/min, and most preferably 5 ℃/min.
Mixing a selenium compound and an organic lithium compound in an organic solvent; the organolithium compound is preferably n-butyllithium; the mass-volume ratio of the selenium compound to the organic lithium compound is preferably (60 to 100) mg:1ml, more preferably (70 to 90) mg:1ml, more preferably 80mg:1ml; the organic solvent is preferably n-hexane; the preferred ratio of the selenium compound to n-hexane is 10mg: (2 to 15) ml, more preferably 10mg: (4-12) ml, more preferably 10mg: (6-10) ml, most preferably 10mg:8ml of the solution; in the invention, preferably, the selenium compound is mixed with the organic solvent, then the protective gas is introduced, and then the organic lithium compound is added; the protective gas is preferably nitrogen; the time for introducing the protective gas is preferably 5 to 20min, more preferably 8 to 15min, and still more preferably 10min.
After mixing, heating and reacting in a protective atmosphere; the temperature of the heating reaction is preferably 60-80 ℃, and more preferably 70-80 ℃; the heating reaction time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and further preferably 3 hours; in order to avoid volatilization of the organic solvent, the reaction is preferably carried out in an apparatus provided with a condensing reflux in the present invention.
After the reaction, the reaction product is preferably cooled to room temperature, washed with an organic solvent and dried to obtain the lithium insertion type selenium compound.
The lithium insertion type selenium compound is prepared by lithium insertion, the preparation method is simple, the obtained product has high porosity, large specific surface area and selenium vacancy, and the lithium insertion type selenium compound has high activity and high stability in an electrolytic water reaction by utilizing the composite effect.
The invention also provides a lithium insertion type selenium compound prepared by the method; (ii) a The particle size of the lithium insertion type selenium compound is preferably 400-600 nm; the lithium insertion type selenium compound is a material with a porous structure.
The invention also provides an application of the lithium insertion type selenium compound prepared by the method as a water electro-catalytic decomposition catalyst.
Wherein, the electrocatalytic water decomposition catalyst can be a hydrogen absorption reaction catalyst or an oxygen evolution reaction catalyst; the solution may have a pH of 0 to 14 when water is decomposed by electrocatalysis, and more preferably water is decomposed by electrocatalysis at a pH of 0, a pH of 7 and a pH of 14.
In order to further illustrate the present invention, the following embodiments are provided to describe the lithium insertion selenium compound, its preparation method and application in detail.
The reagents used in the following examples are all commercially available.
Example 1
Li-IrSe of the invention 2 The synthesis is divided into two parts, and the first step is solid phase reaction method to synthesize the IrSe block 2 (ii) a Second step Li-IrSe synthesized by lithium ion insertion method 2 。
1.1 solid-phase reaction method for synthesizing IrSe block 2 The particle size is 400 nm-600 nm.
192.2mg of iridium powder and 157.9mg of selenium powder were uniformly mixed and then added to a mortar, and ground for 50min. The ground gray sample was transferred to a quartz tube having a length of 20cm and an inner diameter of 2cm, and the quartz tube was then evacuated to vacuumVacuum degree of 10 -5 torr. Placing the quartz tube with the sample in a muffle furnace under a vacuum state, reacting at 1000 ℃, at a heating rate of 5 ℃/min for 15h, and then naturally cooling to room temperature; taking out the quartz tube, manually shaking for several times, then carrying out reaction at 1000 ℃, heating up at a speed of 5 ℃/min for 15h, washing the obtained product with deionized water for multiple times, and drying the product in a vacuum oven at 60 ℃ to obtain the black block IrSe 2 And (4) obtaining a product.
1.2 bulk IrSe 2 80mg of n-hexane (8 ml) is added into a 50ml three-neck flask; putting the catheter deep into N-hexane solution, and introducing N 2 Aerating for 10min to discharge O in the liquid 2 And the like. Then, 1ml of n-butyllithium was taken out from the glove box by a 2ml syringe and charged into the three-necked flask. The three-neck flask is placed in an oil bath pot, a condensation reflux device is added, and then the temperature of the oil bath pot is raised to 60 ℃ and the reaction time is 3 hours. Naturally cooling to room temperature after reaction, taking out a sample, washing the sample for 4 to 5 times by using normal hexane, and drying the sample in a vacuum oven at the temperature of 60 ℃ to obtain the lithium-inserted selenium compound, namely Li-IrSe 2 。
IrSe coated on the black bulk obtained in example 1 by scanning Electron microscope 2 Analysis was performed to obtain a scanning electron micrograph, as shown in FIG. 1 a.
IrSe coated black bulk IrSe obtained in example 1 by transmission electron microscope 2 Analysis was performed to obtain a transmission electron micrograph, as shown in FIG. 1 b.
As can be seen from FIGS. 1a and 1b, the bulk IrSe obtained by this process is IrSe 2 The grain diameter is between 400nm and 600nm.
Scanning Electron microscope was used to synthesize Li-IrSe obtained in example 1 2 Analysis was performed to obtain a scanning electron micrograph, as shown in FIG. 1 c.
The Li-IrSe obtained in example 1 was subjected to a transmission electron microscope 2 Analysis was performed to obtain a transmission electron micrograph, as shown in FIG. 1 d.
As can be seen from FIGS. 1c and 1d, li-IrSe produced by the method 2 The nano catalyst has the same grain diameter of 400 nm-600 nm and large grain sizeSmall and unchanged, but small holes are produced.
IrSe bulk obtained in example 1 was subjected to X-ray electron diffraction 2 The analysis was carried out to obtain an X-ray electron diffraction pattern thereof, as shown in FIG. 2.
X-ray Electron diffraction on Li-IrSe obtained in example 1 2 The analysis was carried out to obtain an X-ray electron diffraction pattern thereof, as shown in FIG. 2.
As can be seen from FIG. 2, the bulk IrSe obtained in example 1 2 The nano-catalyst has good phase formation, while Li-IrSe 2 The nano catalyst has Li + The introduction of ions resulted in two hetero-peaks of lithium selenate.
EXAMPLE 2 bulk IrSe 2 And Li-IrSe 2 Catalytic performance testing of nanocatalysts
IrSe bulk prepared in example 1 of the present invention 2 And Li-IrSe 2 The nano catalyst is used for carrying out electro-catalysis hydrogen production, oxygen production and full hydrolysis catalytic performance tests.
5mg of IrSe from example 1 2 And Li-IrSe 2 Adding the nano catalyst into a mixed solution of 0.5mL of ethanol, 0.47mL of water and 0.03mL of perfluorosulfonic acid, performing ultrasonic treatment for 45min, dripping 4 mu L of sample on a glassy carbon electrode with the diameter of 3mm, drying, and taking the glassy carbon electrode as a working electrode and placing the glassy carbon electrode on 0.5M H 2 SO 4 The activity of the catalyst as a hydrogen and oxygen producing catalyst for electrochemical decomposition of water was measured in 1.0M PBS and 1.0M KOH solutions.
Regarding the electrochemical decomposition of water to produce hydrogen, the scanning speed of the linear sweep voltammetry is 5mV/s, and the obtained LSV curve is shown in FIG. 3, wherein FIG. 3a is bulk IrSe 2 FIG. 3b shows Li-IrSe as a catalyst 2 Is a catalyst. As can be seen from FIG. 3a, at-10 mA/cm 2 When the bulk is IrSe 2 At 0.5M H 2 SO 4 The overpotentials in 1.0M PBS and 1.0M KOH solutions were 225mV,371mV, and 297mV, respectively. However, as can be seen from FIG. 3b, at-10 mA/cm 2 When Li-IrSe 2 At 0.5M H 2 SO 4 The overpotentials in 1.0M PBS and 1.0M KOH solutions were 55mV,120mV and 72mV, respectively.
For the electrochemical decomposition of water to produce oxygen, the linear sweep voltammetry was performed at a sweep rate of 5mV/s, and the resulting LSV curve is shown in FIG. 4, where FIG. 4a is a plot of bulk IrSe 2 FIG. 4b shows Li-IrSe as a catalyst 2 Is a catalyst. As shown in FIG. 4a, at 10mA/cm 2 Then bulk IrSe 2 At 0.5M H 2 SO 4 The potentials in both 1.0M PBS and 1.0M KOH solutions exceeded 1.7V; however, as shown in b in FIG. three, at 10mA/cm 2 When Li-IrSe 2 At 0.5M H 2 SO 4 The overpotentials in the 1.0M PBS and 1.0M KOH solutions were 220mV,315mV, and 270mV, respectively.
For the catalytic Performance testing of the perhydrolysis, 5mg of the block IrSe obtained in example 1 were used 2 And Li-IrSe 2 Adding the nano catalyst into a mixed solution of 0.5mL of ethanol, 0.47mL of water and 0.03mL of perfluorosulfonic acid, performing ultrasonic treatment for 45min, brushing the sample on 2cm x 2cm C paper, and subjecting the paper to Li-IrSe 2 Inspired by the high HER and OER activity of the invention with Li-IrSe in the same electrolyte 2 The voltammogram of the electrolyzed water reaction obtained by assembling a two-electrode electrolyzed water reaction vessel for the positive electrode and the negative electrode is shown in FIG. 5. As can be seen from FIG. 5, 10mA cm were added to a solution of 0.5M H2SO4,1.0M PBS and 1.0M KOH -2 A voltage of 1.44,1.50 and 1.48V, respectively, is required. To further explore the stability of the catalyst, the present invention tested Li-IrSe 2 The stability profile of the long-term electrochemical process at all pH conditions is shown in fig. 6. As can be seen from FIG. 6, the peak area is at 20mAcm -2 After the continuous operation for 24 hours, the current holding rates of the electrolytic cell are respectively 90%,66% and 91%, and the stability is good. In particular, by gas chromatography, it was found that H 2 And O 2 Is the only gas phase product, and the molar ratio is 2:1 in 24h of water electrolysis, and the total faradaic efficiency is about 100 percent.
Claims (9)
1. A preparation method of a lithium insertion type selenium compound is characterized by comprising the following steps:
mixing a selenium compound and an organic lithium compound in an organic solvent, and heating the mixture in a protective atmosphere to react to obtain a lithium insertion selenium compound; the selenium compound is a selenium compound of platinum group elements;
the selenium compound is selected from iridium diselenide; the grain size of the selenium compound is 400-600 nm;
the temperature of the heating reaction is 60-80 ℃; the heating reaction time is 1-5 h.
2. The method according to claim 1, wherein the mass-to-volume ratio of the selenium compound to the organolithium compound is (60 to 100) mg:1ml.
3. The method according to claim 1, wherein the organolithium compound is n-butyllithium.
4. The method of claim 1, wherein the selenium compound is prepared by the following method: selenium powder and platinum group metal powder are mixed and calcined in vacuum to obtain the selenium compound.
5. The preparation method according to claim 4, wherein the temperature of the vacuum calcination is 950 ℃ to 1150 ℃; the vacuum calcination time is 25-40 h; vacuum degree of vacuum calcination is 10 -4 ～10 -6 torr。
6. The method according to claim 5, wherein the vacuum calcination includes a first vacuum calcination and a second vacuum calcination; after the first vacuum calcination, cooling to room temperature, and then carrying out second vacuum calcination.
7. The lithium insertion selenide prepared according to any one of claims 1 to 6.
8. The use of the lithium insertion selenium compound prepared according to any one of claims 1 to 6 as a catalyst for electrocatalytic decomposition of water.
9. Use according to claim 8, wherein the electrocatalytic decomposition of water has a solution pH of 0 to 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910405725.1A CN110065932B (en) | 2019-05-15 | 2019-05-15 | Lithium insertion type selenium compound, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910405725.1A CN110065932B (en) | 2019-05-15 | 2019-05-15 | Lithium insertion type selenium compound, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110065932A CN110065932A (en) | 2019-07-30 |
| CN110065932B true CN110065932B (en) | 2022-10-28 |
Family
ID=67370789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910405725.1A Active CN110065932B (en) | 2019-05-15 | 2019-05-15 | Lithium insertion type selenium compound, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110065932B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057416B (en) * | 2022-06-14 | 2024-03-26 | 国网湖北省电力有限公司黄石供电公司 | LiIrSeO electrode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275355A (en) * | 2013-05-20 | 2013-09-04 | 中国科学技术大学 | Organic modified molybdenum disulfide nanosheet layer and preparation method thereof |
| CN104310482A (en) * | 2014-09-29 | 2015-01-28 | 南京邮电大学 | Method for preparing molybdenum disulfide nanosheets by ultrasonic-assisted chemical intercalation |
| CN106311282A (en) * | 2016-08-09 | 2017-01-11 | 河南工程学院 | Preparing method of porous monocrystal IT MoS2 nanosheet and application thereof |
| CN107868982A (en) * | 2016-09-28 | 2018-04-03 | 清华大学 | A kind of preparation method of the semi metallic compound of metal platinum |
| CN108579769A (en) * | 2018-04-19 | 2018-09-28 | 清华-伯克利深圳学院筹备办公室 | Composite material, the preparation method and the usage of stratiform two-dimensional material interlayer confinement metal or metallic compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201304770D0 (en) * | 2013-03-15 | 2013-05-01 | Provost Fellows Foundation Scholars And The Other Members Of Board Of | A scalable process for producing exfoliated defect-free, non-oxidised 2-dimens ional materials in large quantities |
| WO2015121682A1 (en) * | 2014-02-17 | 2015-08-20 | Ucl Business Plc | Method for producing dispersions of nanosheets |
-
2019
- 2019-05-15 CN CN201910405725.1A patent/CN110065932B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275355A (en) * | 2013-05-20 | 2013-09-04 | 中国科学技术大学 | Organic modified molybdenum disulfide nanosheet layer and preparation method thereof |
| CN104310482A (en) * | 2014-09-29 | 2015-01-28 | 南京邮电大学 | Method for preparing molybdenum disulfide nanosheets by ultrasonic-assisted chemical intercalation |
| CN106311282A (en) * | 2016-08-09 | 2017-01-11 | 河南工程学院 | Preparing method of porous monocrystal IT MoS2 nanosheet and application thereof |
| CN107868982A (en) * | 2016-09-28 | 2018-04-03 | 清华大学 | A kind of preparation method of the semi metallic compound of metal platinum |
| CN108579769A (en) * | 2018-04-19 | 2018-09-28 | 清华-伯克利深圳学院筹备办公室 | Composite material, the preparation method and the usage of stratiform two-dimensional material interlayer confinement metal or metallic compound |
Non-Patent Citations (2)
| Title |
|---|
| Iridium−Tungsten Alloy Nanodendrites as pH-Universal Water-Splitting Electrocatalysts;Fan Lv et al.;《ACS central science》;20180829;第4卷;第1244-1252页 * |
| Modulation of Hydrogen Evolution Catalytic Activity of Basal Plane in Monolayer Platinum and Palladium Dichalcogenides;Haihua Huang et al.;《ACS Omega》;20180829;第3卷;第10058-10065页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110065932A (en) | 2019-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Audichon et al. | Electroactivity of RuO2–IrO2 mixed nanocatalysts toward the oxygen evolution reaction in a water electrolyzer supplied by a solar profile | |
| Lobyntseva et al. | Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies | |
| CN108315760B (en) | Metal organic framework/foamed nickel electrode material and preparation method and application thereof | |
| Corona-Guinto et al. | Performance of a PEM electrolyzer using RuIrCoOx electrocatalysts for the oxygen evolution electrode | |
| CN109453772B (en) | CrO2-RuO2Solid solution material, preparation method thereof and application of solid solution material as acidic OER electrocatalyst | |
| CN109012749A (en) | Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN111663152B (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
| CN108358181A (en) | A kind of the evolving hydrogen reaction elctro-catalyst and preparation method and application of phosphide | |
| CN110117797B (en) | Electrolytic cell and application thereof in hydrogen production by electrolyzing water | |
| CN111715245A (en) | Based on high catalytic activity and crystalline RuTe2The electrolytic water catalyst and the preparation method thereof | |
| Wang et al. | Boosting catalytic activity of niobium/tantalum-nitrogen active-sites for triiodide reduction in photovoltaics | |
| CN113594479A (en) | Preparation method of Fe and N co-doped porous carbon zinc air battery catalyst | |
| CN113277573A (en) | PEM (proton exchange membrane) electrolyzed water anode catalyst and preparation method thereof | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN107570154B (en) | Iron-based hydrogen production electrocatalyst and preparation method thereof | |
| CN110065932B (en) | Lithium insertion type selenium compound, and preparation method and application thereof | |
| CN111952606A (en) | Fe/HKUST-1 catalyst, and preparation method and application thereof | |
| Lv et al. | N/C doped nano-size IrO2 catalyst of high activity and stability in proton exchange membrane water electrolysis | |
| CN116474772A (en) | Transition metal doped modified flaky iridium oxide catalyst and preparation method and application thereof | |
| CN114086202B (en) | Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production | |
| CN115821319A (en) | Octahedron Cu 2 O/CuO heterojunction catalyst, and 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |