CN105056977A - Hydrogen evolution reaction catalyst and preparation method thereof - Google Patents
Hydrogen evolution reaction catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105056977A CN105056977A CN201510447275.4A CN201510447275A CN105056977A CN 105056977 A CN105056977 A CN 105056977A CN 201510447275 A CN201510447275 A CN 201510447275A CN 105056977 A CN105056977 A CN 105056977A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- preparation
- catalyst
- chalcogen compound
- nanoscale twins
- 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention belongs to the field of catalytic materials, and specifically relates to a hydrogen evolution reaction catalyst and a preparation method thereof, wherein the hydrogen evolution reaction catalyst is a nanometer sheet layer composite material of a transition metal disulfide compound and an oxide thereof. According to the present invention, hydrogen peroxide is added during an ultrasonic peeling process to peel the transition metal disulfide compound into a partially-oxidized nanometer sheet layer, the obtained nanometer sheet layer retains the two-dimensional crystal structure of the transition metal disulfide compound and maintains the high electron transport efficiency of the transition metal disulfide compound, and the partially-oxidized defect structure provides more catalytic activity sites for the hydrogen evolution reaction to increase the area density of the catalytic activity sites of the catalyst so as to finally improve the catalytic activity of the catalyst; and the preparation method has characteristics of simple preparation conditions, easy operation process, low production cost and easy mass production, and the product has high catalytic activity, can replace the platinum noble metal hydrogen evolution catalyst, and has broad application prospects.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to a kind of evolving hydrogen reaction Catalysts and its preparation method.
Background technology
The environmental problem of the world today and energy crisis impel people to go to find reproducible clean energy resource to replace traditional fossil energy, wherein hydrogen energy source due to its wide material sources and combustion product be that water gets most of the attention.Up to the present, hydrogen energy source mainly still derives from water decomposition hydrogen manufacturing, and the efficiency therefore how improving water decomposition hydrogen manufacturing just becomes key issue the most urgently to be resolved hurrily.Generally speaking, business-like liberation of hydrogen catalyst is mainly based on metal platinum now, but metal platinum is expensive and contamination resistance and service life all very poor, this just causes the high cost of hydrogen energy source industry, hinders the large-scale practical application of this green regenerative energy sources.Recently, researcher finds that the combination of transition metal two chalcogen compound and hydrogen can be close with metal platinum, thus thinks that it is expected to substituted metal platinum as efficient evolving hydrogen reaction catalyst in theory.Experimental result subsequently also confirms that these compounds effectively catalytic water can decompose generation hydrogen really.Such as: " American Chemical Society's catalysis material " (ACSCatalysis2013,3,2101-2107) with " naturally chemistry " (NatureChemistry2013,5,263-275) magazine just reports transition metal two chalcogen compound nanoscale twins can as very efficient evolving hydrogen reaction catalyst.In addition, " nanometer communication " (NanoLetters2013,13,3426-3433) magazine also demonstrates the catalytic activity that two selenizing molybdenums and two tungsten selenide also have high evolving hydrogen reaction.
But transition metal two chalcogen compound bulk material is compared with metallic platinum catalyst, and also there is clearly defect, namely their active site is less, this severely limits its application.Fortunately, these materials are all piled up by lamella and are formed, thus on the one hand can by peeling off method improves its specific area and active catalyst sites density." science " (Science2011,331,568) magazine has just been reported for work first with an organic solvent can peel off these transition metal two chalcogen compounds under ultrasonic, obtains monolithic or a few lamella nanoscale twins.On the other hand, in order to increase the active site of these materials further, researcher also introducing hetero-atoms carries out doping treatment, such as " materials chemistry " (JournalofMaterialsChemistryA2014,2,5597-5601) be doped to by sulphur atom in two selenizing molybdenum nanoscale twins, the defect sturcture that foreign atom is introduced serves the effect of active site, greatly improves the catalytic activity for hydrogen evolution of material.But general doping method all needs at high temperature to carry out, severe reaction conditions, is unfavorable for extensive preparation and commercial applications.
The present invention uses hydrogen peroxide as oxidant, by partial oxidation while that transition metal two chalcogen compound being in liquid phase stripping process, obtains part oxidized transition metal two chalcogen compound nanoscale twins material.The composite prepared not only retains higher electron transport ability, and also add its catalytic active site dot density due to the doping of oxygen atom.Experimental result shows that these catalyst have extraordinary evolving hydrogen reaction catalytic performance, its performance is close to business-like metallic platinum catalyst, and due to preparation method simple, equipment requirement is low, makes it have good large-scale commercial and produces and prospect of the application.
Summary of the invention
The object of the present invention is to provide a kind of evolving hydrogen reaction Catalysts and its preparation method of catalytic performance excellence.
Evolving hydrogen reaction catalyst provided by the invention is the nanoscale twins composite of a kind of transition metal two chalcogen compound and oxide thereof.The concrete steps of its preparation method are:
(1) 1 ~ 3g transition metal two chalcogen compound solid is placed in 90 ~ 150mL organic solvent, adds the hydrogen peroxide of 1% ~ 5wt% of organic solvent weight, ultrasonic disperse 3 ~ 5 hours, leave standstill;
(2) supernatant after leaving standstill is outwelled, lower floor's solid is disperseed in organic solvent again, then ultrasonic disperse 3 ~ 5 hours, standing, obtain upper strata nanoscale twins dispersion liquid;
(3) nanoscale twins dispersion liquid is carried out vacuum drying or dialysis, then freeze drying, namely obtain the nanoscale twins composite of transition metal two chalcogen compound and oxide thereof, finished product is pressed powder.
In the present invention, described transition metal two chalcogen compound is the one in molybdenum bisuphide, two selenizing molybdenums, or is both mixture.
In the present invention, described transition metal two chalcogen compound and the size of oxidate nano lamella thereof are 20 ~ 200nm, and thickness is 1 ~ 5nm.
In the present invention, described organic solvent is the one in 1-METHYLPYRROLIDONE, DMF, isopropyl alcohol, or wherein several mixtures.
The composite of evolving hydrogen reaction catalyst prepared by the inventive method and transition metal two chalcogen compound and oxide thereof, as oxidant, transition metal two chalcogen compound is carried out partial oxidation by hydrogen peroxide, this can not only keep the electrical conductivity efficiency of evolving hydrogen reaction catalyst nano lamella, the active site of catalyst can also be increased, and the final catalytic activity improving catalyst.
Preparation condition of the present invention is simple, and operating process is convenient, and production cost is lower, is easy to mass production; And universality is strong, is applicable to evolving hydrogen reaction catalyst, can replaces platinum class noble metal liberation of hydrogen catalyst, have wide industrial applications prospect.
Accompanying drawing explanation
fig. 1.the two selenizing molybdenums prepared and the atomic force microscope images of oxidate nano lamella composite thereof.
fig. 2.the two selenizing molybdenums prepared and the transmission electron microscope picture of oxidate nano lamella composite thereof.
fig. 3.the two selenizing molybdenums prepared and the results of elemental analyses of oxidate nano lamella composite thereof.
fig. 4.the two selenizing molybdenums prepared and the evolving hydrogen reaction catalytic performance figure of oxidate nano lamella composite thereof.
fig. 5.the evolving hydrogen reaction catalytic performance figure of the molybdenum bisuphide prepared and oxidate nano lamella composite thereof.
Detailed description of the invention
Further describe preparation and the catalytic hydrogen evolution reactivity worth thereof of the nanoscale twins composite of evolving hydrogen reaction catalyst transition metal two chalcogen compound of the present invention and oxide thereof by the following examples.But this embodiment is only illustrate as providing instead of limit the present invention.
embodiment 1
Get 1g bis-selenizing molybdenum powder and be placed in 100mL isopropyl alcohol, add 2wt% hydrogen peroxide ultrasonic 5 hours, outwell supernatant after leaving standstill and add 100mL isopropyl alcohol more then more ultrasonic 5 hours, after leaving standstill, get the dispersion liquid of upper strata nanoscale twins 50
oin C vacuum drying oven, vacuum drying obtains nanoscale twins compound to remove residual solvent in 3 days.
As can see from Figure 1, the two selenizing molybdenums prepared and the lamellar spacing of oxidate nano lamella composite very little, edge is irregular and have some pore structures, illustrate its exist more defect may part oxidized, and specific area is larger.As can be seen from Figure 2 prepared nanoscale twins still remains with the crystal structure of two selenizing molybdenums, the interplanar distance wherein can observing nanoscale twins in Fig. 2 a is 0.68nm, corresponding to the feature interplanar distance of two selenizing molybdenums, the spacing of lattice can observing part nanoscale twins in Fig. 2 b is 0.285nm, corresponding to the Characteristic Lattice spacing of (100) crystal face of two selenizing molybdenums, as can be seen from Figure 3 in obtained nanoscale twins, the tetravalence molybdenum atom of script is partially oxidized becomes sexavalence molybdenum atom, demonstrate gained nanoscale twins material partially oxidized, as can be seen from the catalytic performance in Fig. 4, the two selenizing molybdenums prepared and the initial catalyst voltage of oxidate nano lamella composite thereof reach 75mV, relatively business-like metallic platinum catalyst.
embodiment 2
Get 1g molybdenum disulfide powder and be placed in 120mL isopropyl alcohol, add 2wt% hydrogen peroxide ultrasonic 4 hours, outwell supernatant after leaving standstill and add 120mL isopropyl alcohol more then more ultrasonic 4 hours, after leaving standstill, get the dispersion liquid of upper strata nanoscale twins 50
oin C vacuum drying oven, vacuum drying obtains nanoscale twins compound to remove residual solvent in 4 days.
As can be seen from Figure 5 the catalytic performance of molybdenum bisuphide and oxidate nano lamella composite thereof also has very big raising compared to molybdenum disulfide nano sheet layer itself, illustrates that this is a kind of universal method that can be used for the catalytic activity of hydrogen evolution improving transition metal two chalcogen compound.
Therefore the catalyst that prepared by our method has extraordinary evolving hydrogen reaction catalytic performance, and its performance can compare favourably with traditional metallic platinum catalyst.
embodiment 3
Get 1g bis-selenizing molybdenum powder and be placed in 150mLN-methyl pyrrolidone, add 5wt% hydrogen peroxide ultrasonic 3 hours, outwell supernatant after leaving standstill and add 150mLN-methyl pyrrolidone more then more ultrasonic 3 hours, the dispersion liquid getting upper strata nanoscale twins after leaving standstill is placed in water dialysis 5 days with except desolventizing and other water-solubility impurities.Finally the freeze-drying of product freeze drier is obtained product.
embodiment 4
Get 1g bis-selenizing molybdenum powder and be placed in 110mLN, in dinethylformamide, add 1wt% hydrogen peroxide ultrasonic 4 hours, outwell supernatant after leaving standstill and add 110mLN again, dinethylformamide then more ultrasonic 4 hours, the dispersion liquid getting upper strata nanoscale twins after leaving standstill is placed in water dialysis 6 days with except desolventizing and other water-solubility impurities.Finally the freeze-drying of product freeze drier is obtained product.
embodiment 5
Get 1g molybdenum disulfide powder and be placed in 90mL isopropyl alcohol, add 4wt% hydrogen peroxide ultrasonic 4 hours, outwell supernatant after leaving standstill and add 100mL isopropyl alcohol more then more ultrasonic 4 hours, after leaving standstill, get the dispersion liquid of upper strata nanoscale twins 50
oin C vacuum drying oven, vacuum drying obtains nanoscale twins compound to remove residual solvent in 2 days.
embodiment 6
Get 1g bis-selenizing molybdenum powder and be placed in 110mL isopropyl alcohol, add 3wt% hydrogen peroxide ultrasonic 3 hours, outwell supernatant after leaving standstill and add 110mL isopropyl alcohol more then more ultrasonic 3 hours, after leaving standstill, get the dispersion liquid of upper strata nanoscale twins 40
oin C vacuum drying oven, vacuum drying obtains nanoscale twins compound to remove residual solvent in 3 days.
The preparation-obtained composite materials of embodiment 2-6, has similar structural character with the composite materials obtained by embodiment 1, all can be used as desirable evolving hydrogen reaction catalyst.
Claims (5)
1. a preparation method for the nanoscale twins composite of evolving hydrogen reaction catalyst transition metal two chalcogen compound and oxide thereof, is characterized in that concrete steps are:
(1) 1 ~ 3g transition metal two chalcogen compound solid is placed in 90 ~ 150mL organic solvent, adds the hydrogen peroxide of 1% ~ 5wt% of organic solvent weight, ultrasonic disperse 3 ~ 5 hours, leave standstill;
(2) supernatant after leaving standstill is outwelled, lower floor's solid is disperseed in organic solvent again, then ultrasonic disperse 3 ~ 5 hours, standing, obtain upper strata nanoscale twins dispersion liquid;
(3) nanoscale twins dispersion liquid is carried out vacuum drying or dialysis, then freeze drying, namely obtain the nanoscale twins composite of transition metal two chalcogen compound and oxide thereof, finished product is pressed powder.
2. preparation method according to claim 1, is characterized in that transition metal two chalcogen compound described in step (1) is the one in molybdenum bisuphide, two selenizing molybdenums, or is both mixture.
3. preparation method according to claim 1, it is characterized in that the size of transition metal two chalcogen compound described in step (1) and oxidate nano lamella thereof is 20 ~ 200nm, thickness is 1 ~ 5nm.
4. preparation method according to claim 1, is characterized in that the organic solvent described in step (1) is the one in 1-METHYLPYRROLIDONE, DMF, isopropyl alcohol, or wherein several mixtures.
5. the composite of evolving hydrogen reaction catalyst transition metal two chalcogen compound prepared by one of claim 1 ~ 4 preparation method and oxide thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510447275.4A CN105056977A (en) | 2015-07-28 | 2015-07-28 | Hydrogen evolution reaction catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510447275.4A CN105056977A (en) | 2015-07-28 | 2015-07-28 | Hydrogen evolution reaction catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105056977A true CN105056977A (en) | 2015-11-18 |
Family
ID=54486616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510447275.4A Pending CN105056977A (en) | 2015-07-28 | 2015-07-28 | Hydrogen evolution reaction catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105056977A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597785A (en) * | 2016-01-25 | 2016-05-25 | 温州大学 | Method for preparing efficient copper-doped MoS2 nano-sheet array electrocatalyst |
| CN106099053A (en) * | 2016-06-03 | 2016-11-09 | 东华大学 | A kind of molybdenum sulfide/selenizing molybdenum composite material and preparation thereof and application |
| CN106994360A (en) * | 2017-04-05 | 2017-08-01 | 江苏大学 | A kind of preparation method of Z configurations visible light catalytic decomposition water composite |
| CN108671942A (en) * | 2018-04-04 | 2018-10-19 | 山东大学 | A kind of catalyst molybdenum disulfide and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104495935A (en) * | 2014-12-03 | 2015-04-08 | 安徽百特新材料科技有限公司 | Preparation method of molybdenum disulfide nanosheet in stripping manner |
-
2015
- 2015-07-28 CN CN201510447275.4A patent/CN105056977A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104495935A (en) * | 2014-12-03 | 2015-04-08 | 安徽百特新材料科技有限公司 | Preparation method of molybdenum disulfide nanosheet in stripping manner |
Non-Patent Citations (3)
| Title |
|---|
| JIN-MUN YUN等: "Exfoliated and Partially Oxidized MOS2 Nanosheets by One-Pot Reaction for Efficient and Stable Organic Solar Cells", 《SMALL》 * |
| JUNFENG XIE等: "Controllable Disorder Engineering in Oxygen-Incorporated MoS2 Ultrathin Nanosheets for Effcient Hydrogen Evolution", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 刘培生: "《多孔材料引论》", 30 September 2004 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597785A (en) * | 2016-01-25 | 2016-05-25 | 温州大学 | Method for preparing efficient copper-doped MoS2 nano-sheet array electrocatalyst |
| CN105597785B (en) * | 2016-01-25 | 2017-12-22 | 温州大学 | A kind of efficient Copper-cladding Aluminum Bar MoS2The preparation method of nano-chip arrays elctro-catalyst |
| CN106099053A (en) * | 2016-06-03 | 2016-11-09 | 东华大学 | A kind of molybdenum sulfide/selenizing molybdenum composite material and preparation thereof and application |
| CN106994360A (en) * | 2017-04-05 | 2017-08-01 | 江苏大学 | A kind of preparation method of Z configurations visible light catalytic decomposition water composite |
| CN108671942A (en) * | 2018-04-04 | 2018-10-19 | 山东大学 | A kind of catalyst molybdenum disulfide and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | In situ fabrication of 2D/3D g-C3N4/Ti3C2 (MXene) heterojunction for efficient visible-light photocatalytic hydrogen evolution | |
| Shaari et al. | Carbon and graphene quantum dots in fuel cell application: An overview | |
| JP6047742B2 (en) | Iron phthalocyanine / graphene nanocomposite, iron phthalocyanine / graphene nanocomposite-supported electrode, and methods for producing them | |
| Cui et al. | Mo2C nanoparticles decorated graphitic carbon sheets: biopolymer-derived solid-state synthesis and application as an efficient electrocatalyst for hydrogen generation | |
| Zhang et al. | One-step solvothermal synthesis of graphene/Mn3O4 nanocomposites and their electrochemical properties for supercapacitors | |
| de Oliveira et al. | Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems | |
| CN109701572B (en) | FeCo/MXene compound and preparation method and application thereof | |
| Davis et al. | Silver‐graphene nanoribbon composite catalyst for the oxygen reduction reaction in alkaline electrolyte | |
| Inamdar et al. | Sulfur-containing carbon by flame synthesis as efficient metal-free electrocatalyst for oxygen reduction reaction | |
| Liu et al. | Constructing one-dimensional silver nanowire-doped reduced graphene oxide integrated with CdS nanowire network hybrid structures toward artificial photosynthesis | |
| CN106602092B (en) | Preparation method and application of single-walled carbon nanotube hollow sphere oxygen reduction catalyst | |
| Lu et al. | Monolithic 3D cross-linked polymeric graphene materials and the likes: preparation and their redox catalytic applications | |
| Zhang et al. | Preparation of graphene supported nickel nanoparticles and their application to methanol electrooxidation in alkaline medium | |
| CN105056977A (en) | Hydrogen evolution reaction catalyst and preparation method thereof | |
| CN104801319A (en) | Hydrogen evolution reaction catalyst nanosheet layer-graphene three-dimensional composite material and preparation method thereof | |
| Bahru et al. | Allotrope carbon materials in thermal interface materials and fuel cell applications: a review | |
| KR101983457B1 (en) | Fe-N-C ELECTROCATALYST, METHOD OF MANUFACTURNING THE SAME AND FUEL CELL COMPRISING Fe-N-C ELECTROCATALYST | |
| Liu et al. | Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation | |
| CN104103829B (en) | MoS2Nanometer sheet/graphene composite nano material with holes and preparation method | |
| Huang et al. | Well-dispersive Pt nanoparticles grown on 3D nitrogen-and sulfur-codoped graphene nanoribbon architectures: highly active electrocatalysts for methanol oxidation | |
| Babu et al. | Facile synthesis of graphene/N-doped carbon nanowire composites as an effective electrocatalyst for the oxygen reduction reaction | |
| Song et al. | A palladium doped 1T-phase molybdenum disulfide–black phosphorene two-dimensional van der Waals heterostructure for visible-light enhanced electrocatalytic hydrogen evolution | |
| Feng et al. | Ultrathin Ti 3 C 2 nanosheets served as a highly efficient hole transport layer on a Fe 2 O 3 photoanode for photoelectrochemical water oxidation | |
| Li et al. | Recent progress on the interfacial regulation and application of 2D antimonene-based van der Waals heterostructures | |
| Shen et al. | Graphited carbon black curled nanoribbons simultaneously boosted stability and electrocatalytic activity of 1T-MoS2/MoO3 toward hydrogen evolution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151118 |