CN105177621B - Molybdenum-oxygen cluster modified hollow microspherical nickel disulfide catalyst and application thereof - Google Patents
Molybdenum-oxygen cluster modified hollow microspherical nickel disulfide catalyst and application thereof Download PDFInfo
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- CN105177621B CN105177621B CN201510701910.7A CN201510701910A CN105177621B CN 105177621 B CN105177621 B CN 105177621B CN 201510701910 A CN201510701910 A CN 201510701910A CN 105177621 B CN105177621 B CN 105177621B
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- 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
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Abstract
The invention discloses a molybdenum-oxygen cluster modified hollow microspherical nickel disulfide catalyst and application thereof to the aspect of producing hydrogen and oxygen through electric catalytic cracking of water, belonging to the technical field of electric catalytic cracking of water. A target material can be obtained through carrying out one-step hydrothermal reaction on raw materials including a surfactant, a sulfur source, a molybdenum source and a metal nickel substrate. The preparation method is simple and controllable, the raw materials are cheap, the sample property repeatability is good, the time consumed in the synthesis process is short, the requirement for equipment is not high, and the molybdenum-oxygen cluster modified hollow microspherical nickel disulfide catalyst is suitable for large-scale production. Particularly, the material can be simultaneously subjected to water electrolysis in an alkaline electrolysis tank to generate hydrogen and oxygen (namely fully-hydrolyzed water), has the current density of 10mA/cm<2> when the voltage is 1.45V, has higher activity than fully-hydrolyzed water of precious metal platinum and ruthenium oxide, is one of best double-surface catalysts at present, can greatly increase the electric energy to chemical energy conversion efficiency and meets the national requirements for saving energy and reducing emission.
Description
Technical field
The invention belongs to electro-catalysis splitting water technical field, and in particular to a kind of nickel micron of curing three of molybdenum oxygen cluster modification
Hollow ball catalyst and its application in terms of electro-catalysis cracks aquatic products hydrogen and produces oxygen.
Background technology
As fossil fuel energy is depended in the development of social economy, people unduly, environmental pollution and global warming are exacerbated,
And fossil fuel faces exhaustion, so a kind of alternative green energy resource of searching is extremely urgent, and Hydrogen Energy becomes only choosing.
The electric energy that can not be stored being transformed by solar energy, wind energy and water energy etc. can be converted into Hydrogen Energy by electro-catalysis splitting water, as
The hydrogen of carrier both can be used for storing energy, it is also possible to directly as important industrial chemicals.But, in actual electrolysis water
During need to overcome larger overpotential, cause energy utilization rate significantly to decline, and active catalyst can be reduced effectively
The overpotential of electrolysis water, so as to improve the utilization rate of electric energy.At present, platinum, the noble metal of palladium class and iridium, rhodium base oxide are respectively
Maximally effective electro-catalysis cracking aquatic products hydrogen and product VPO catalysts, but the extremely low shortcoming of its expensive, reserves are severely impacted
The extensive application of such material, therefore, exploitation high activity, the non-precious metal catalyst of earth's crust rich reserves cause the wide of people
It is general to bar up.
In recent years, more highly active base metal electrochemical cleavage water catalyst, for example, efficient water-splitting are occurred in that
Produce hydrogen catalyst molybdenum bisuphide (J.Am.Chem.Soc.2005 127 volume page 5308)；And VPO catalysts phosphatization cobalt is produced in water-splitting
(Science 2008 year volume 32 page 1072).Although most elctro-catalysts show excellent under strong acid or basic conditions
Catalytic property, producing hydrogen end yet with them can not match completely with the optimal condition of work for producing oxygen end, can neither be same
Use in individual electrolytic cell.Therefore, synthesis can be used to producing hydrogen under identical condition of work and can be used to produce the two-sided electro-catalysis of oxygen again
Agent remains a huge challenge.
The content of the invention
The present invention is for the purpose of improving electric energy and be converted into the efficiency of energy utilization of chemical energy, it is proposed that the two of molybdenum oxygen cluster modification
Vulcanize three nickel micrometre hollow sphere catalyst and its application in terms of electro-catalysis cracks aquatic products hydrogen and produces oxygen.
A kind of nickel micrometre hollow sphere catalyst of curing three of molybdenum oxygen cluster modification of the present invention, it is characterised in that：It is
Surfactant, sulphur source and molybdenum source is soluble in water, resulting solution is loaded into reactor, metal nickel substrate is subsequently adding, heat
Prepare after reaction 12h~24h.
Described surfactant be water-soluble triblock copolymer, including but not limited to P123, F127 etc. and its
Mixture.
Described sulphur source includes but is not limited to thiocarbamide, thioacetamide and its derivative or its mixture.
Described molybdenum source be water-soluble molybdenum salt, including but not limited to ammonium molybdate, sodium molybdate, four thio ammonium molybdate and its
Mixture.
Described metal nickel substrate includes but is not limited to the metallic nickel materials such as nickel foam, nickel screen and nickel foil.
Described sulphur source is 2.4~14.4 with the mol ratio of molybdenum element with element sulphur in molybdenum source：1；Element sulphur is lived with surface
Property agent mol ratio be 17.4~34.9：1, heating-up temperature is 160~220 DEG C.
The nickel micrometre hollow sphere catalyst of curing three of prepared molybdenum oxygen cluster modification both can be used as electro-catalysis splitting water
The negative pole of hydrogen is produced, the positive pole that electro-catalysis cracks aquatic products oxygen is can be used for again, be a kind of bifunctional water-splitting catalyst.
Beneficial effect
Present invention contrast prior art has following innovative point：
1. synthesis material is cheap, and synthesis temperature is low, and synthesis step is simple, and controllability is high, properties of samples favorable reproducibility.
2. the micron that the nickel of curing three of gained molybdenum oxygen cluster modification is constructed with ultra-thin (thickness about 1.3nm) nanometer sheet is hollow
Ball (a diameter of 500nm~1 μm) fractions distribution in metal nickel substrate, ultrathin nanometer piece structure of this length in metal nickel substrate
The micrometre hollow sphere built, greatly improves the electrochemical catalysis area and mass-transfer efficiency of resulting materials.
3. resulting materials are a kind of new electro-catalysis water-splitting catalyst, are all shown in full pH value range (0~14)
Excellent catalysis activity and stability, it is 106mV that in the basic conditions (pH is 14) electrolysis aquatic products hydrogen produces oxygen not in overpotential
During with 136mV, current density can reach 10mA/cm2, and stable performance.When voltage is 1.45V, current density just can reach
To 10mA/cm2, it is one of two-sided electro-catalysis water-splitting catalyst best at present.
4. resulting materials can carry out water-splitting without the need for binding agent directly as working electrode, improve the electricity of elctro-catalyst
Sub- transfer rate, reduces electric energy loss, improves the efficiency of energy utilization for converting electrical energy into chemical energy.
Description of the drawings
Fig. 1：The XRD spectra of the Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1；
Fig. 2：The Raman spectrograms of the Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1；
Fig. 3：The SEM pictures of the Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1；
Fig. 4：The Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1 is in acid (pH is 0, schemes A), neutrality
Electro-catalysis splitting water (deionized water) H2-producing capacity in (pH is 7, schemes B), alkalescence (pH is 14, schemes C) electrolyte, i.e. electric current is close
Degree is with relative to reversible hydrogen electrode potential change curve；
Fig. 5：The Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1 is in acid (pH is 0, schemes A), neutrality
In (pH is 7, scheme B), alkalescence (pH is 14, schemes C) electrolyte under gained catalytic stability curve, i.e. constant voltage, current density with
Time changing curve；
Fig. 6：The Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1 is in alkaline (pH is 14) electrolyte
Electro-catalysis splitting water (deionized water) produce the polarization curve (figure A) and catalytic stability curve (scheming B) of oxygen；
Fig. 7：The Raney nickel of curing three of the molybdenum oxygen cluster modification obtained in embodiment 1 is in alkaline electrolytic bath as two-sided
The polarization curve (figure A) and stability curve (figure B) of elctro-catalyst electrolysis water.
Specific embodiment
With reference to the accompanying drawings and examples the invention will be further described, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
The P123 of 10mg ammonium molybdates, 45mg thioacetamides and 0.15g is dissolved in into 30mL deionized waters, 60mL reactions are added
In kettle, nickel foam (thickness 1.5mm, volume density 0.23mg/cm are then placed in3), 200 DEG C of reaction 24h are obtained molybdenum oxygen cluster and repair
The nickel micrometre hollow sphere catalyst of curing three of decorations.
Some structural characterizations have been carried out to catalyst prepared by said method.Fig. 1 by acquisition catalyst XRD spectra,
Go out that peak position is consistent with PDF#44-1418 in the spectrogram, show the Ni that the catalyst is six sides3S2；Fig. 2 is to be obtained catalyst
Raman spectrograms, it can be seen that gained catalyst be MoOxThe Ni of modification3S2；Fig. 3, can be with to be obtained catalyst SEM photograph
Find out the micrometre hollow sphere that the catalyst is ultrathin nanometer piece composition.
Electro-catalysis cracking aquatic products hydrogen is carried out in standard three electrode electrolytic cell to catalyst prepared by said method and produces oxygen
Matter is tested；In electrolytic cell working electrode be the present invention prepare molybdenum oxygen cluster modification the Raney nickel of curing three, reference electrode be
Saturated calomel electrode, to electrode be carbon-point.It should be noted that all with saturated calomel electrode as reference electricity in electro-catalysis test
The potential that pole obtains is converted into reversible hydrogen electrode potential in property figure.And the complete solution water in alkaline electrolytic bath is electric two
Test under limited condition, the Raney nickel of curing three of the molybdenum oxygen cluster modification of synthesis is respectively as electrolysis aquatic products hydrogen end and product oxygen
End.
Fig. 4 is that in acidity, (pH is 0,0.5M H to the catalyst2SO4), it is neutral that (pH is 7,1M K2HPO4With 1M KH2PO4Press
Corresponding proportion mixes), gained electro-catalysis cracking aquatic products hydrogen and produce oxygen property figure in alkaline (pH is 14,1M KOH) electrolyte, can
To find out：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 123mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 192mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 106mV, the catalyst current density reaches 10mA/cm2；
The above results show that all there is the catalyst excellent electro-catalysis to produce hydrogen activity in full pH value range.
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 136mV, the catalyst current density reaches 10mA/cm2。
Fig. 5 is catalyst gained electrolysis water in acid (pH is 0), neutral (pH is 7), alkaline (pH is 14) electrolyte
Produce hydrogen and alkalescence produces oxygen catalytic stability property figure, added overpotential is respectively 0.12V, 0.19V, 0.11V, 0.15V；Can see
Go out, (10~20mA/cm under larger current density conditions2), material works for (200 hours) through long-time, its catalytic performance
Keep stable.
Fig. 6 for the property of the electro-catalysis water-splitting of complete solution water in catalyst alkalescence (pH is 14,1M KOH) electrolytic cell and
Stability, it can be seen that：
Under the conditions of pH is for 14, after composition electrolytic cell, when institute's making alive is 1.45V, the catalyst current density reaches
10mA/cm2, and work within (100 hours) through long-time, its catalytic performance does not have any change.
Embodiment 2
It is same as Example 1, it is simply 60mg by the quantitative change of ammonium molybdate.The electrocatalysis characteristic of gained catalyst：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 153mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 182mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 126mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 143mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell；
Under the conditions of pH is for 14, when institute's making alive is 1.51V, the catalyst current density reaches 10mA/cm2。
Embodiment 3
Same as Example 1, simply reaction temperature is changed into 160 DEG C.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 158mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 190mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 140mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 155mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell：
Under the conditions of pH is for 14, when institute's making alive is 1.53V, the catalyst current density reaches 10mA/cm2。
Embodiment 4
It is same as Example 1, simply the consumption of surfactant is changed into into 0.3g.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 160mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 188mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 156mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 162mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell：
Under the conditions of pH is for 14, when institute's making alive is 1.55V, the catalyst current density reaches 10mA/cm2。
Embodiment 5
It is same as Example 1, simply will reduce in the reaction time to 12h.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 133mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 192mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 121mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 138mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell：
Under the conditions of pH is for 14, when institute's making alive is 1.5V, the catalyst current density reaches 10mA/cm2。
Embodiment 6
It is same as Example 1, simply ammonium molybdate is changed into into sodium molybdate.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 143mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 191mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 137mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 153mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell；
Under the conditions of pH is for 14, when institute's making alive is 1.52V, the catalyst current density reaches 10mA/cm2。
Embodiment 7
It is same as Example 1, simply thioacetamide is changed into into thiocarbamide.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 131mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 194mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 117mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 128mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell；
Under the conditions of pH is for 14, when institute's making alive is 1.48V, the catalyst current density reaches 10mA/cm2。
Embodiment 8
It is same as Example 1, only nickel foam is changed into into nickel foil piece.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 156mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 206mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 146mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 183mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell；
Under the conditions of pH is for 14, when institute's making alive is 1.57V, the catalyst current density reaches 10mA/cm2。
Embodiment 9
It is same as Example 1, only P123 is changed into into F127.The electrocatalysis characteristic of gained sample：
Electro-catalysis cracks aquatic products hydrogen；
Under the conditions of pH is for 0, when overpotential is 139mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 7, when overpotential is 198mV, the catalyst current density reaches 10mA/cm2；
Under the conditions of pH is for 14, when overpotential is 127mV, the catalyst current density reaches 10mA/cm2；
Electro-catalysis cracks aquatic products oxygen；
Under the conditions of pH is for 14, when overpotential is 158mV, the catalyst current density reaches 10mA/cm2；
After composition electrolytic cell；
Under the conditions of pH is for 14, when institute's making alive is 1.54V, the catalyst current density reaches 10mA/cm2。
Above-mentioned embodiment is only presently preferred embodiments of the present invention, but protection scope of the present invention is not limited to
This, the change that any those familiar with the art can readily occur within the spirit and principles in the present invention is replaced
And improvement, all should cover within the scope of the present invention.
Claims (5)
1. the nickel micrometre hollow sphere catalyst of curing three that a kind of molybdenum oxygen cluster is modified, it is characterised in that：It is by surfactant, sulphur
Source and molybdenum source are soluble in water, and resulting solution is loaded into reactor, are subsequently adding metal nickel substrate, make after heating response 12h~24h
It is standby to obtain；Sulphur source is 2.4~14.4 with the mol ratio of molybdenum element with element sulphur in molybdenum source：1, element sulphur rubs with surfactant
You are than being 17.4~34.9：1, heating-up temperature is 160~220 DEG C；Wherein, surfactant is water-soluble triblock copolymer
Thing, sulphur source is thiocarbamide, thioacetamide and its derivative or its mixture, and molybdenum source is ammonium molybdate, sodium molybdate, four thio ammonium molybdate
Or its mixture.
2. the nickel micrometre hollow sphere catalyst of curing three that a kind of molybdenum oxygen cluster as claimed in claim 1 is modified, it is characterised in that：
Surfactant is P123 or F127.
3. the nickel micrometre hollow sphere catalyst of curing three that a kind of molybdenum oxygen cluster as claimed in claim 1 is modified, it is characterised in that：
Metal nickel substrate is nickel foam, nickel screen or nickel foil.
4. a kind of nickel micrometre hollow sphere catalyst of curing three of the molybdenum oxygen cluster modification described in claims 1 to 3 any one exists
Application in terms of electrolysis water.
5. a kind of nickel micrometre hollow sphere catalyst of curing three of molybdenum oxygen cluster modification as claimed in claim 4 is in terms of electrolysis water
Application, it is characterised in that：The negative pole or the positive pole as electro-catalysis cracking aquatic products oxygen of aquatic products hydrogen are cracked as electro-catalysis.
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| CN108179433B (en) * | 2016-12-08 | 2019-09-06 | 中国科学院大连化学物理研究所 | Ordered mesopore carbon loads nanometer iridium base electrocatalytic hydrogen evolution electrode and its preparation and application |
| CN107968208B (en) * | 2017-12-01 | 2020-09-25 | 吉林大学 | Nano lamellar structure of trinickel disulfide/molybdenum disulfide composite material and preparation method thereof |
| CN109055972B (en) * | 2018-07-20 | 2020-05-12 | 曲阜师范大学 | Mn doped Ni3S2Nano-array hydrogen evolution catalyst and preparation method and application thereof |
| CN110931268B (en) * | 2019-11-22 | 2022-09-02 | 浙江工业大学 | Oxygen-sulfur doped Ni-Mo bimetallic material for super capacitor and preparation method thereof |
| CN111686821A (en) * | 2020-06-22 | 2020-09-22 | 南京邮电大学 | Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid |
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