CN106637288B - A kind of nitrogen mixes phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load and preparation method thereof - Google Patents
A kind of nitrogen mixes phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load and preparation method thereof Download PDFInfo
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- CN106637288B CN106637288B CN201611223255.XA CN201611223255A CN106637288B CN 106637288 B CN106637288 B CN 106637288B CN 201611223255 A CN201611223255 A CN 201611223255A CN 106637288 B CN106637288 B CN 106637288B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to electro-catalysis hydrogen producing technology field, specially a kind of nitrogen mixes phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load and preparation method thereof.Catalyst entirety of the present invention is diametrically 100 ~ 200 nanometers of shaggy nanowire structure, activated centre β-Mo2The particle diameter distribution of C is 2 ~ 10 nanometers, and is closely embedded in the graphite surface of N doping, and phosphorus is then equably doped into β-Mo by way of phosphorus molybdenum key2In C-structure；It is MoO that nitrogen, which mixes graphite,xPolyaniline in the polyaniline hybridized presoma of phytic acid-mixes graphite by the nitrogen generated in place during high temperature cabonization.The catalyst shows high electro-catalysis hydrogen production activity and stability in acid condition, and preparation method is easy to operate and Modulatory character is strong, and cost of material is cheap, and production process risk is low, is suitable for large-scale production and the hydrogen manufacturing of industrial electrolysis water.
Description
Technical field
The invention belongs to electro-catalysis hydrogen producing technology fields, and in particular to a kind of phosphorus doping molybdenum carbide that nitrogen mixes mineral carbon load is received
Rice noodles electro-catalysis catalyst for preparing hydrogen and preparation method thereof.
Background technique
Hydrogen is a kind of important raw material of industry, is widely used in petrochemical industry, electronics industry, metallurgical industry, fine organic
The fields such as synthesis, aerospace.In addition, high energy density, excellent combustibility, cleanliness without any pollution (combustion that hydrogen has
Burning product is only water) the advantages that become the best substitute of traditional fossil energy.Currently, industrial hydrogen production technique seriously according to
Rely fossil energy, main method is Effect of Catalysis In Petrochemistry cracking and natural gas steam reformation hydrogen production, these process energy consumptions are very high, simultaneously
The generation and discharge of GHG carbon dioxide are difficult to avoid that, from increasingly serious at present environmental pressure and total energy approach
Angle considers, and does not meet the energy development strategy of " Green Sustainable ", seriously constrains hydrogen as a kind of cleaning energy
Application of the source in new energy field.In recent years, new-generation technology is developed rapidly, such as solar power generation, wind-force hair
Electricity, nuclear energy power generation, hydroelectric generation, geothermal power generation etc., so that previous was considered as that the water electrolysis hydrogen production technology of high energy consumption is drawn again
The highest attention of Qi Liao scientific circles, water electrolysis hydrogen production technology are even described as " optimal work by many scientists and enterprisers
Industry hydrogen production process ".
The key problem of water electrolysis hydrogen production technology is efficient, high stability and cheap hydrogen manufacturing elctro-catalyst exploitation.Carbon
Change molybdenum (MoCx) it is a kind of widest base metal hydrogen manufacturing elctro-catalyst of current research, because its cheap, considerable catalysis is living
Property, high stability, simple synthetic method and the wide in range pH scope of application, become current research hotspot.Currently, carbon
The synthesis process for changing molybdenum inevitably uses high temperature (~ 800 DEG C), inevitably will cause molybdenum carbide in synthesis process
The sintering and reunion of grain are difficult to realize the Superfine powder structure of high uniformity dispersion；In addition, molybdenum carbide (β-Mo2C hydrogen) is inhaled
Attached Gibbs free energy (Δ GH*) it is -0.26eV, it is too strong to result in Mo-H key, it is suppressed that the Heyrovsky mistake in hydrogen production reaction
Journey, to inhibit β-Mo2The electro-catalysis hydrogen production activity of C.Therefore, it is badly in need of developing new molybdenum carbide synthetic method, to control height
β-Mo in temperature synthesis2The reunion and sintering of C exposes β-Mo by the method for nanometer engineering as far as possible2C increases activity in hydrogen production process
The quantity of position, to improve the electro catalytic activity of catalyst entirety.Furthermore, it is necessary to other components be introduced, to β-Mo2The electronics of C
Structure is regulated and controled, its Δ G is improvedH*To weaken Mo-H key, β-Mo is inherently improved2The electro-catalysis hydrogen production activity of C.
Summary of the invention
An object of the present invention is to provide the phosphorus doping molybdenum carbide nano wire electro-catalysis hydrogen manufacturing that a kind of nitrogen mixes mineral carbon load
Catalyst.The catalyst raw material is from a wealth of sources, low in cost, and shows high electro-catalysis hydrogen production activity in acid condition
And stability, it can replace and use most wide platinum based catalyst at this stage.
The phosphorus doping molybdenum carbide nano wire electro-catalysis for mixing mineral carbon load the second object of the present invention is to provide a kind of above-mentioned nitrogen
The preparation method of catalyst for preparing hydrogen.This method mentality of designing is clearly novel, and preparation process is easy to operate and Modulatory character is strong, production
Process risk is low, is suitable for large-scale production.
The present invention utilizes the structure directing effect of phytic acid and the acid-base reaction of phytic acid and aniline, first control synthesis
Phytic acid-polyaniline (PA-PANI) hybridized nanowire；Then, using between the amino in molybdate and Pa-PANI hybridized nanowire
Electrostatic attraction effect, by MoOxIt is connected on above-mentioned PA-PANI hybridized nanowire, generates MoOxPhytic acid-polyaniline (MoOx-
PA-PANI) three component hybridized nanowire presoma.In the carbonisation of above-mentioned hybridized nanowire presoma, the ammonia in polyaniline
Base can be used as nitrogen source, phytic acid makees phosphorus source, and utilize MoOx" the sub-nanometer of MoOx and organic matter in-PA-PANI hydridization presoma
Contact ", overcomes Mo during high―temperature nuclei2The reunion of C nano particle, so that a kind of prepared above-mentioned nitrogen mixes mineral carbon load
Phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen there is very distinct structure feature and advantage: the catalyst is integrally in
Reveal the shaggy nanowire structure that diameter is 100 ~ 200 nanometers, activated centre β-Mo2C(molybdenum carbide) particle diameter distribution
It is 2 ~ 10 nanometers, and is closely embedded in the graphite surface of N doping, phosphorus is then equably doped into β-by way of phosphorus molybdenum key
Mo2In C-structure.Further, since MoOxThe composition of-PA-PANI hydridization presoma is controllable, can pass through phytic acid in regulation presoma
Content can be realized and carry out accuracy controlling (0.001 ~ 6 wt %) to the content of the phosphorus adulterated in final elctro-catalyst.The electricity is urged
Ultra-dispersed nano silicon carbide molybdenum in agent composition can sufficiently expose its catalytic active site；Nitrogen, which mixes graphite, can effectively improve electro-catalysis
The electric conductivity of agent accelerates charge transfer rate in electrochemical process；Phosphorus doping can effectively improve the electronics of molybdenum carbide fermi level
Cloud density weakens Mo-H bond strength, to improve the latent active of activated centre molybdenum carbide.The above structure and electronics characteristic make
The catalyst shows high electro-catalysis hydrogen production activity and stability in acid condition.
Nitrogen provided by the invention mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load, whole to present
The shaggy nanowire structure that diameter is 100 ~ 200 nanometers out, activated centre β-Mo2C(molybdenum carbide) particle diameter distribution be 2
~ 10 nanometers, and it is closely embedded in the graphite surface of N doping, phosphorus is then equably doped into β-Mo by way of phosphorus molybdenum key2C
In structure；It is MoO that the nitrogen, which mixes graphite,xPolyaniline in the polyaniline hybridized presoma of phytic acid-is by during high temperature cabonization
The nitrogen generated in place mixes graphite.
The nitrogen provided by the invention mixes the system of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load
Preparation Method, specific steps are as follows:
(a) initiator is made using ammonium persulfate, phytic acid makees structure directing agent, and the molar ratio for regulating and controlling phytic acid and aniline is
(0.001 ~ 1), is polymerize by Oxidation at room temperature, obtains a series of phytic acid-polyaniline (PA-PANI) hybridized nanowire presomas 1；
(b) then, above-mentioned presoma 1 and ammonium molybdate aqueous solution are utilized into molybdate and forerunner in 45-50 DEG C of continuation hydridization
Electrostatic attraction effect between amino in body 1, by MoOxIt is connected on above-mentioned hydridization presoma 1, generates MoOxPhytic acid-polyphenyl
Amine (MoOx- PA-PANI) hybridized nanowire presoma 2；
(c) under argon gas protection, above-mentioned hydridization presoma 2 is carbonized 1 ~ 12 hour under the conditions of 600 ~ 1100 DEG C, heating speed
Rate control is 1 ~ 50 DEG C/min, can be prepared by the nitrogen and mix the phosphorus doping molybdenum carbide nano wire electro-catalysis hydrogen manufacturing of mineral carbon load urging
Agent.
In step (a), the molar ratio of phytic acid and aniline preferably 0.025 ~ 0.1.
In step (c), carburizing temperature is preferably 800 DEG C ~ 900 DEG C, and heating rate is preferably 2 ~ 10 DEG C/min, carbonization time
Preferably 3 ~ 5 hours.
Nitrogen of the invention mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load, can be used for acid item
Water electrolysis hydrogen production reaction under part, but the catalyst is not intended to limit for being catalyzed other catalytic hydrogenations and hydrogenolysis.
The present invention has the advantages that compared with prior art
1, the present invention makes full use of MoOxPhytic acid-polyaniline (MoOx- PA-PANI) MoO in hydridization presomaxWith organic matter
" sub-nanometer contact ", overcome Mo during high―temperature nuclei2The reunion of C nano particle, so that prepared above-mentioned nitrogen is mixed
Activated centre β-the Mo of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load2C(molybdenum carbide) distribution it is equal
Even, partial size is only 2 ~ 10 nanometers, and is closely embedded in the surface that nitrogen mixes graphite carrier.In addition, aniline not only may act as carbon source but also
It can be used as nitrogen source；Phytic acid can be used as effective phosphorus source, MoOxThe monoblock type homogeneous texture of-PA-PANI hydridization presoma and controllable
Composition, so that being that the molybdenum carbide activated centre for producing uniform phosphorus doping and nitrogen are mixed only by a step high temperature cabonization process
Graphite carrier, and phosphorus is equably to be doped into β-Mo by way of phosphorus molybdenum key2In C-structure.The carbonization that this method is prepared
Molybdenum elctro-catalyst no matter β-the Mo made from the catalyst2The partial size and dispersibility in the activated centre C, or from the structure of phosphorus doping,
And nitrogen mixes the raising of graphite bring elctro-catalyst electric conductivity, all has apparent advantage than previous preparation method.
2, the source of the phosphorus in the method for phosphorus doping catalyst is prepared in the past, there are mainly three types of: a) it is passed through in carbonisation
Toxic PH3Gas makees phosphorus source；B) sodium hypophosphite is added on to doped samples side in carbonisation, passes through the height of sodium hypophosphite
Temperature decomposites the PH come3Gas makees phosphorus source；C) phosphorus doping to sample is realized while using phosphomolybdic acid as the source Mo.But it is above-mentioned
Three kinds of methods all have inevitable great drawback: risk is too high (a and b), absolute uncontrollable (c) of the doping of phosphorus,
And it is related to multiphase gas-solid reaction in carbonisation, lead to inhomogeneities (a and b) of the doping of phosphorus etc..The present invention utilizes plant
Acid is used as phosphorus source, using the method for organic inorganic hybridization, so that phosphorus source, carbon source, nitrogen source and molybdenum source come into full contact with, by step height
The catalyst of Uniform Doped can be realized in temperature conversion；Simultaneously as organic inorganic hybridization presoma (MoOx- PA-PANI) group
At controllable, can be can be realized by the content of phosphorus source (phytic acid) in regulation presoma to the phosphorus adulterated in final elctro-catalyst
Content carries out accuracy controlling；In addition, the very strong PH of the obstructed toxicity of the doping process3Or explosive sodium hypophosphite is used, it is whole
The lower carbonization of inert gas Ar protection, risk are extremely low.
3, nitrogen prepared by the present invention mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load, is utilized
Ultra-dispersed nanostructure, nitrogen mix the good electric conductivity of graphite and the phosphorus doping regulation β-Mo of uniform, controllable2The activated centre C
Electronic structure, substantially reduce the catalyst water electrolysis hydrogen production reaction in overpotential, greatly improve electro-catalysis hydrogen manufacturing
Activity and stabill.
4, the present invention can be prepared above-mentioned nitrogen and mix graphite by " multicomponent nanocomposite hydridization presoma high temperature cabonization method "
The phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of load.The prices of raw materials of the preparation method are cheap, and technique at
Ripe stabilization, easy to operate and low risk, controllability are strong, are suitable for large-scale production.
Detailed description of the invention
Fig. 1 (a) is the scanning for the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen that the nitrogen mixes mineral carbon load
Electron microscope is (b) transmission electron microscope picture of the catalyst, (c) is the high-resolution-ration transmission electric-lens figure of the catalyst, (d) is the catalysis
The distribution diagram of element of agent.
Fig. 2 left figure is that the nitrogen mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load 0.5
mol/L H2SO4Polarization curve in electrolyte (acidity).
Fig. 3 is that the nitrogen mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load 0.5
mol/L H2SO4The polarization curve of 3000 front and backs of circulation in electrolyte.
Specific embodiment
The present invention is further described below by specific embodiment, but is not intended to limit the present invention.
Embodiment 1 takes the aniline of 2 mmol to be placed in a beaker with 0.1 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 5 hours to 850 DEG C, heating speed
Rate is controlled in 2 DEG C/min, can be prepared by the phosphorus doping molybdenum carbide nano wire electro-catalysis producing hydrogen, catalyzing that the nitrogen mixes mineral carbon load
Agent.As shown in Figure 1: by the super-dispersed nano Mo of phosphorus doping2C(2 ~ 10 nanometer) composition, and the nanoparticle is closely embedded in nitrogen
It mixes on graphite.
Nitrogen obtained mix the electro-chemical test of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load by
Following steps carry out:
(a) the phosphorus doping molybdenum carbide nano wire electro-catalysis producing hydrogen, catalyzing that nitrogen described in 30 mg mixes mineral carbon load is accurately weighed
Agent be dispersed in include the deionized water of 750 μ L, the dehydrated alcohol of 250 μ L and 80 μ L Nafion solution (5%) mixing
In solution, ultrasound 1 hour to form uniform suspension.Then the 4 above-mentioned hanging drops of μ L is taken to be coated onto the glass carbon that diameter is 3 mm
On electrode (GC), working electrode can be prepared in natural drying；
(b) the electrochemistry hydrogen manufacturing performance test for the working electrode being prepared is all made of three-electrode system, electrolyte 0.5
The sulfuric acid solution (acidity) of mol/L.It is graphite rod to electrode, reference electrode is saturated calomel electrode (Saturated
Calomel electrode, SCE), (CHI760E, Shanghai China occasion instrument are public in electrochemical workstation for linear sweep voltammetry curve
Department) on carry out, test temperature is room temperature, and sweep speed is 5 mV/s, and scanning range is -0.1 to -0.6 V, and experimental data is equal
Carry out IR correction.Electrode potential is obtained by comparing saturated calomel electrode, and is converted into relative to reversible hydrogen electrode
The electrode potential of (Reversible hydrogen electrode, RHE), conversion equation are as follows: ERHE=ESCE + 0.059
pH + 0.241。
As shown in Fig. 2, the elctro-catalyst shows high hydrogen evolution activity in acid condition, current density is -10
mA/cm2Under conditions of overpotential be only -89 mV；As shown in figure 3, the elctro-catalyst equally shows high analysis in acidity
Stabilized hydrogen does not observe apparent activity decline after 3000 circulations.
Embodiment 2 takes the aniline of 2 mmol to be placed in a beaker with 0.2 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 45 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 5 hours to 850 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in 2 DEG C/min, the nitrogen for being made described.
The electro-chemical test that nitrogen obtained mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load is same
The step of case study on implementation 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -129 mV.
Embodiment 3 takes the aniline of 2 mmol to be placed in a beaker with 0.15 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 5 hours to 850 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen system of mineral carbon load in 2 DEG C/min, the nitrogen for being made described
The nitrogen obtained mixes the electro-chemical test of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load with case study on implementation 1
Step (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -145 mV.
Embodiment 4 takes the aniline of 2 mmol to be placed in a beaker with 0.5 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 5 hours to 850 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen system of mineral carbon load in 2 DEG C/min, the nitrogen for being made described
The nitrogen obtained mixes the electro-chemical test of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load with case study on implementation 1
Step (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -177 mV.
Embodiment 5 takes the aniline of 2 mmol to be placed in a beaker with 0.3 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 5 hours to 850 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in 2 DEG C/min, the nitrogen for being made described.
The electro-chemical test that nitrogen obtained mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load is same
The step of case study on implementation 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -197 mV.
Embodiment 6 takes the aniline of 2 mmol to be placed in a beaker with 0.1 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 3 hours to 800 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in 2 DEG C/min, the nitrogen for being made described.System
The nitrogen obtained mixes the electro-chemical test of the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load with case study on implementation 1
Step (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -143 mV.
Embodiment 7 takes the aniline of 2 mmol to be placed in a beaker with 0.1 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 3 hours to 700 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in 2 DEG C/min, the nitrogen for being made described.
The electro-chemical test that nitrogen obtained mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load is same
The step of case study on implementation 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -163 mV.
Embodiment 8 takes the aniline of 2 mmol to be placed in a beaker with 0.1 mmol phytic acid, and the stirring of 10 ml deionized waters is added
10 minutes are stood after 30 minutes again；The ammonium persulfate aqueous solution that 5 g mass concentrations are 8.4%, room temperature are added into above-mentioned standing liquid
After standing reaction 12 hours, it is washed with deionized 4 times for use.Solid product after above-mentioned washing is placed in 40 g mass concentrations
For in 5.8% ammonium molybdate aqueous solution, 50 DEG C are reacted 6 hours.After reaction, it by above-mentioned suspension centrifugal drying, obtains
MoOxPhytic acid-polyaniline (MoOx- PA-PANI) presoma.
By above-mentioned presoma as in tube furnace, under argon gas protection, temperature programming is carbonized 3 hours to 1000 DEG C, heating speed
Rate control mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in 2 DEG C/min, the nitrogen for being made described.
The electro-chemical test that nitrogen obtained mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load is same
The step of case study on implementation 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is respectively -176 mV.
In conclusion nitrogen prepared by the present invention mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load
Using MoOx- phytic acid-polyaniline (MoOx- PA-PANI) it is preceding as hydridization presoma, pass through argon gas and protects lower high temperature cabonization
It is made.Preparation method utilizes MoOxMoO in-PA-PANI hydridization presomaxWith " the Ya Na of organic matter (phytic acid and aniline)
Rice property contacts " and controllable feature is formed, overcome β-Mo during high―temperature nuclei2The reunion in the activated centre C, so that preparation
Obtained electro-catalysis catalyst for preparing hydrogen has very distinct structure feature and advantage: the nitrogen mixes the phosphorus doping carbon of mineral carbon load
Change molybdenum nano wire electro-catalysis catalyst for preparing hydrogen and integrally show the shaggy nanowire structure that diameter is 100 ~ 200 nanometers,
Activated centre β-Mo2C(molybdenum carbide) particle diameter distribution be 2 ~ 10 nanometers, and be closely embedded in the graphite surface of N doping, phosphorus
Then β-Mo is equably doped by way of phosphorus molybdenum key2In C-structure.The phosphorus doping of the catalyst can effectively change β-Mo2C
Electronic structure and improve its latent active, ultra-fine nanostructure can preferably expose catalytic active site, closely inlay knot
Structure can effectively improve the electric conductivity of elctro-catalyst to accelerate charge transfer rate in electrochemical process, and accelerate generate hydrogen and
It is living to show high electro-catalysis hydrogen manufacturing to reduce the resistance to mass tranfer during electro-catalysis in acid condition for the diffusion of electrolyte
Property and stability.The technological operation is simple and Modulatory character is strong, and cost of material is cheap, and production process risk is low, is suitable for big rule
Mould production.
Above content is only the basic explanation under present inventive concept, and any etc. made by technical solution according to the present invention
Effect transformation, is within the scope of protection of the invention.
Claims (7)
1. the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen that a kind of nitrogen mixes mineral carbon load, it is characterised in that: whole to be in
The shaggy nanowire structure that diameter is 100 ~ 200 nanometers, activated centre β-Mo2The particle diameter distribution of C is 2 ~ 10 nanometers, and
It is closely embedded in the graphite surface of N doping, phosphorus is then equably doped into β-Mo by way of phosphorus molybdenum key2In C-structure；Nitrogen
Mixing graphite is MoOxPolyaniline in the polyaniline hybridized presoma of phytic acid-is mixed by the nitrogen generated in place during high temperature cabonization
Graphite.
2. a kind of nitrogen as described in claim 1 mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load
Preparation method, which is characterized in that specific steps are as follows:
(a) initiator is made using ammonium persulfate, phytic acid makees structure directing agent, and the molar ratio for regulating and controlling phytic acid and aniline is
(0.001 ~ 1), is polymerize by Oxidation at room temperature, obtains a series of polyaniline hybridized nanowire precursor 1 of phytic acid-；
(b) then, above-mentioned presoma 1 and ammonium molybdate aqueous solution are utilized into molybdate and presoma 1 in 45-50 DEG C of continuation hydridization
In amino between electrostatic attraction effect, by MoOxIt is connected on above-mentioned hydridization presoma 1, generates MoOxPhytic acid-polyaniline
Hybridized nanowire presoma 2；
(c) under argon gas protection, above-mentioned hybridized nanowire presoma 2 is carbonized 1 ~ 12 hour under the conditions of 600 ~ 1100 DEG C, is heated up
Rate control is 1 ~ 50 DEG C/min, can be prepared by the phosphorus doping molybdenum carbide nano wire electro-catalysis hydrogen manufacturing that the nitrogen mixes mineral carbon load
Catalyst.
3. preparation method as claimed in claim 2, which is characterized in that in step (a), the molar ratio of phytic acid and aniline is
0.025~0.1。
4. the preparation method as described in claim 2, which is characterized in that in step (c), carburizing temperature is 800 DEG C ~ 900 DEG C.
5. the preparation method as described in claim 2, which is characterized in that heating rate is 2 ~ 10 DEG C/min in step (c).
6. the preparation method as described in claim 2, which is characterized in that carbonization time is 3 ~ 5 hours in step (c).
7. nitrogen as described in claim 1 mixes the phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load in acidity
Under the conditions of water electrolysis hydrogen production reaction in application.
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| CN107999108B (en) * | 2017-12-13 | 2019-01-18 | 中国石油大学(华东) | Molybdenum carbide or tungsten carbide catalyst of a kind of load of nitrogen-phosphor codoping carbon and its preparation method and application |
| CN112495408B (en) * | 2018-05-11 | 2022-05-10 | 重庆文理学院 | Preparation method of electrocatalytic hydrogen evolution nano material |
| CN109136973B (en) * | 2018-08-28 | 2020-07-14 | 南京工业大学 | Non-noble metal doped molybdenum carbide hydrogen evolution electrode and preparation method and application thereof |
| CN109675599B (en) * | 2018-12-05 | 2020-09-01 | 华南农业大学 | Nitrogen-doped carbon-coated molybdenum carbide and preparation method and application thereof |
| CN111282588A (en) * | 2018-12-09 | 2020-06-16 | 中国科学院大连化学物理研究所 | Catalyst for hydrogen evolution by electrolyzing water and preparation method and application thereof |
| CN109821563A (en) * | 2019-04-03 | 2019-05-31 | 青岛科技大学 | A kind of preparation method of water electrolysis hydrogen production catalyst |
| CN110368969B (en) * | 2019-08-20 | 2022-04-01 | 南昌航空大学 | Preparation method and application of heteroatom-doped molybdenum carbide hydrogen evolution catalyst loaded on carbon paper or carbon cloth |
| CN111807367A (en) * | 2020-05-07 | 2020-10-23 | 武汉理工大学 | In-situ carbon compounded alpha-Mo2C nanowire and preparation method and application thereof |
| CN113198455B (en) * | 2021-05-17 | 2022-12-09 | 南昌航空大学 | Molybdenum trioxide/molybdenum mesh photocatalyst and preparation method and application thereof |
| CN114457378B (en) * | 2022-03-08 | 2023-04-28 | 中国石油大学(华东) | Preparation method of polyacid derived atomic-level doped molybdenum nitride electrocatalyst |
| CN114904546B (en) * | 2022-05-17 | 2023-08-22 | 江西师范大学 | Ni/P-Mo@Mo for producing hydrogen by ammonia borane hydrolysis 2 C composite nano catalyst and preparation method and application thereof |
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