CN110182784A - A kind of adjustable iron-containing N doping Lauxite base carbon material in aperture and preparation method thereof - Google Patents
A kind of adjustable iron-containing N doping Lauxite base carbon material in aperture and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to adjustable iron-containing N doping Lauxite base carbon materials in a kind of aperture and preparation method thereof, formalin is added in urea liquid, molysite is added after mixing evenly, until solution ph is 2~4, obtain reaction solution, reaction solution reaction generates sediment, obtains Fe-UFC presoma after sediment is separated after post treatment；Wherein the molar ratio of urea and formaldehyde is 1:(0.1~1.2)；Fe-UFC presoma is calcined into 2~3h under 700~1000 DEG C of protective atmospheres, obtains the adjustable iron-containing N doping Lauxite base carbon material in aperture.The present invention successfully synthesizes Fe-UFC composite material in the case where not adding any surfactant using direct charring, and methods experiment process is simple, at low cost, iron content is controllable, and nitrogen content is high, and product aperture is adjustable, morphology controllable.
Description
Technical field
The invention belongs to electro-catalysis technical field, in particular to a kind of adjustable iron-containing N doping Lauxite base in aperture
Carbon material and preparation method thereof.
Background technique
The rapid exhausted and environmental pollution of novel fossil fuel promotes us to find sustainable and clean energy resources.
Chemical energy can be converted into electric energy by direct methanol fuel cell (DMFC), and possess energy density it is high, it is pollution-free, fortune
A kind of the advantages that trip temperature is lower, it is considered to be up-and-coming portable and auxiliary power unit technology.In addition, DMFC
Fuel be liquid methanol, methanol transports and stores convenient and safe, and fuel supplement is rapid, and cheap.Currently, DMFC has
There are very big application potential, such as portable power, electric car power supply etc..However, oxygen reduction reaction (ORR) power of cathode
Learn slowly, methanol tolerant poison performance is poor, common Pt or Pt base catalyst it is at high cost be obstruction DMFC commercialized development it is main
Obstacle.So it is very urgent for preparing the base metal base cathod catalyst that ORR catalytic performance is good, methanol tolerant poisons, at low cost
's.
Non-precious metal catalyst, especially transition metal oxide are proved to be a kind of preferable high-performance metal oxidation
Object substitute.However, catalytic performance is catalyzed lower than noble metal base due to the low electric conductivity and utilization rate of transition metal oxide
Agent is restricted in practical applications.In addition, containing more certainly containing heteroatomic graphitization carbon-supported catalysts (such as N, S)
By pi-electron, be conducive to the activation of oxygen molecule.It has recently been demonstrated that being entrained in the transition metal M in N- doping carbon-based material
(such as Fe, Co, Ni) catalytic activity with higher, especially iron-N-C composite catalyst have preferable methanol tolerant ability, and
And there is high electric conductivity and utilization rate.And traditional iron-N-C composite material and preparation method thereof has complexity, at high cost, nitrogen content
It is low, the disadvantages of pattern is uncontrollable, and aperture is single.
Amino resins is very important one of thermoset synthetic resin, and the yield of Lauxite accounts for about global amino resins
80%, be mostly important and amino resins that is being most widely used.Lauxite is opaque thermosetting plastics or resin,
Have many advantages, such as that preparation cost is low, solidification temperature is mild.Lauxite also can be used as the organosilane precursor for preparing N doping porous carbon
Body.Presoma of the Lauxite as carbon material, can not only be used for carbon source, but also as nitrogen source.Traditional Lauxite is with urine
Element and formaldehyde are raw material, and formic acid is catalyst, by what is be prepared under the polymerization reaction room temperature of formaldehyde and urea, then passes through charcoal
Change handles to obtain Lauxite base carbosphere (UFC).
Summary of the invention
It is an object of the invention to overcome problems of the prior art, a kind of adjustable iron-containing nitrogen in aperture is provided and is mixed
Miscellaneous Lauxite base carbon material and preparation method thereof synthesizes iron-containing N doping Lauxite base carbon materials using direct charring
Material,.
In order to achieve the above object, the present invention adopts the following technical scheme:
The following steps are included:
(1) formalin is added in urea liquid, adds molysite after mixing evenly, until solution ph 2~
4, reaction solution is obtained, reaction solution reaction generates sediment, obtains Fe-UFC presoma after sediment is separated after post treatment；Its
The molar ratio of middle urea and formaldehyde is 1:(0.1~1.2)；
(2) Fe-UFC presoma is calcined to 2~3h under 700~1000 DEG C of protective atmospheres, obtains the adjustable iron content in aperture
N doping Lauxite base carbon material.
Further, in step (1), the volumetric concentration of the formalin used is 37%；Urea liquid is every 120mL water
The middle urea that 92.7mmol is added is formulated.
Further, molysite includes Fe(NO3)39H2O.
Further, in step (1), reaction solution stands reaction 1h~6h at room temperature.
Further, in step (1), separation is centrifuge separation；Post-processing is successively to be cleaned and dried, solidified and secondary
It is cleaned and dried.
Further, be cleaned and dried and secondary cleaning drying be by sediment undergoes washing to supernatant pH value for 6.5~
7.5, then in 60 DEG C of dry 12h.
Further, solidification is that the sediment after drying is solidified 48h in 2mol/L hydrochloric acid solution.
Further, calcining carries out in tube-type atmosphere furnace, and heating rate is 1 DEG C/min.
Further, protective atmosphere is argon gas.
According to the adjustable iron-containing N doping Lauxite base carbon material in aperture made from preparation method as described above.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention is added in urea liquid with formalin, Fe-UFC presoma is made under molysite cooperation, and with Fe-
Lauxite in UFC presoma is as carbon source and nitrogen source, using direct charring, in the feelings for not adding any surfactant
Under condition, Fe-UFC composite material is successfully synthesized.The method of the present invention experimentation is simple, at low cost, iron content is controllable, nitrogen content
Height, product aperture is adjustable, morphology controllable, improves oxygen reduction catalyst material property, has to hydrogen reduction catalytic performance is improved
Critically important meaning.Document is searched for, not yet someone utilizes Fe (NO so far for discovery3)3·9H2O is catalyst, prepares iron-containing nitrogen
Lauxite base carbosphere (Fe-UFC) Lai Gaishan hydrogen reduction catalytic performance of doping, the present invention are to pass through conducting base hydridization
Means provide a kind of new method to the promotion of the catalytic activity of oxide type catalyst.
Further, the present invention is with Fe (NO3)3·9H2O is catalyst and source of iron, and raw material is simple.
Further, the present invention makes material keep original pattern when high-temperature calcination by solidification process.
In material produced by the present invention, microstructure is about 3 μm of diameter of flower-shaped porous microsphere, and the pore diameter range of ball is
13nm~99nm, porous microsphere are made of bending nanometer sheet, and nanometer sheet is connected with each other, and iron is not only present in piece in the form of doping
Among layer, and the sheet surfaces for thering is a large amount of iron oxide to be grown in Fe-UFC microballoon.The present invention is it further in fuel electricity
The application in the fields such as pond and lithium oxygen battery is laid a good foundation.Using the resulting Fe-UFC composite material of the present invention as direct methanol
The cathod catalyst of fuel cell, anode catalyst PtRu/C, fuel are the mixed solution of 4M KOH and 5M methanol.Room temperature
Under, cell discharge performance is tested with battery test system, at room temperature its maximum power density 13.99~
18.25mW/cm2。
Detailed description of the invention
Fig. 1 is the XRD diagram of Fe-UFC composite material.
Fig. 2 is the SEM figure of Fe-UFC composite material, and wherein Fig. 2 (a) is the SEM figure of 30000 times of next microballoons, Fig. 2
It (b) is schemed in the SEM of 110000 times of lower Fig. 2 (a) microballoon lamellas.
Fig. 3 is the EDS element surface scan figure of Fe-UFC composite material, and wherein Fig. 3 (a) is the figure of multiple microballoon TEM, Fig. 3
(b) be the region Fig. 3 (a) carbon distribution map；Fig. 3 (c) is the nitrogen distribution map in the region Fig. 3 (a)；Fig. 3 (d) is Fig. 3 (a)
The oxygen element distribution map in region；Fig. 3 (e) is the ferro element distribution map in the region Fig. 3 (a).
Fig. 4 is the cathod catalyst using Fe-UFC as direct methanol fuel cell, anode catalyst PtRu/C, fuel
For the mixed solution of 4M KOH and 5M methanol, battery performance figure at room temperature.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawing.
Preparation method of the present invention, includes the following steps:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, and clear solution is formed under stirring, then plus
Entering suitable volumetric concentration is 37% formaldehyde, makes molar ratio 1:(0.1~1.2 of urea and formaldehyde), after mixing evenly, it is added
Appropriate Fe(NO3)39H2O (Fe (NO3)3·9H2O), ferric nitrate is dissolved in water and shows acidity, the more more more slant acidity added, directly
It is 2~4 to solution ph, appropriate stirring is uniformly mixed solution.Then, solution stands reaction 1h~6h at room temperature, will sink
Starch is centrifuged, and 6500r/min for several times, is done with ultrapure water eccentric cleaning until supernatant pH value is 6.5~7.5,60 DEG C
Dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution, solidification process can make material in high-temperature calcination
When keep original pattern；Later, sediment is subjected to eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until
Supernatant pH value is about 6.5~7.5, and Fe-UFC presoma is obtained after 60 DEG C of oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2~3h in the tube-type atmosphere furnace under 700~1000 DEG C of argon gas,
Heating rate is 1 DEG C/min, is cooled to room temperature and takes out product, obtains Fe-UFC composite material.
Embodiment one
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, and clear solution is formed under stirring, then plus
Entering suitable volumetric concentration is 37% formaldehyde, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate nine
Nitric hydrate iron (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution is in room
Temperature is lower to stand reaction 1.5h, and sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
PH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will precipitate
Object carries out eccentric cleaning, and 6500r/min for several times, until supernatant pH value is about 6.5-7.5, is dried with ultrapure water eccentric cleaning at 60 DEG C
Fe-UFC presoma is obtained after the dry 12h of case.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Fig. 1 is the XRD diagram of Fe-UFC, there is a wide diffraction maximum at 2 θ=23 °, and (002) corresponding to graphitic carbon is brilliant
Face.
Fig. 2 is the SEM figure of Fe-UFC composite material, and wherein Fig. 2 (a) is the SEM figure of 30000 times of next microballoons, Fig. 2
It (b) is schemed in the SEM of 110000 times of lower Fig. 2 (a) microballoon lamellas.Fe-UFC is about 3 μm of a diameter of flower-shaped porous microsphere, ball
Pore diameter range be 13nm~99nm, porous microsphere is made of bending nanometer sheet, and nanometer sheet is connected with each other, and sheet surfaces are raw
Have a large amount of little particle.
Fig. 3 is the EDS Element area profile of Fe-UFC composite material, it was demonstrated that it is multiple that C, N, O, Fe are evenly distributed in Fe-UFC
In condensation material.
Embodiment two
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 3, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment three
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 4, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Comparative example 1
1 is set by pH value, other conditions are the same as embodiment 1.
Referring to Fig. 4, by embodiment 1-3 and comparative example 1 under the conditions of pH value is respectively 1,2,3 and 4 resulting Fe-
Cathod catalyst of the UFC as direct methanol fuel cell, anode catalyst PtRu/C, fuel are 4M KOH and 5M methanol
Mixed solution, at room temperature, using new prestige BTS400 type battery test system (China Shenzhen Xin Li Science and Technology Ltd.) to battery
Discharge performance is tested.By test analysis, its maximum power density is as shown in table 1 below at room temperature.
Fe-UFC made from 1 embodiment 1-3 of table is surveyed as the battery performance of the cathod catalyst of direct methanol fuel cell
Examination
| Embodiment | 1 | 2 | 3 | Comparative example 1 |
| Maximum power density (mW/cm2) | 18.25 | 17.09 | 13.99 | 12.15 |
As shown in Table 1, cathod catalyst of the Fe-UFC produced by the present invention as direct methanol fuel cell, the electricity of assembling
Pond maximum power density is in 13.99~18.25mW/cm2.The content of added ferric nitrate is different, and products therefrom pattern and iron contain
Amount is different, and it is 2 in pH value that when pH value is between 2~4, the battery maximum power density of assembling is gradually decreased with pH value increase
When maximum power density value it is maximum, when pH value reduces, the battery maximum power density of assembling sharply declines.
Example IV
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.1 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment five
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.8 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment six
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:1.2 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment seven
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 4h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
PH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will precipitate
Object carries out eccentric cleaning, and 6500r/min for several times, until supernatant pH value is about 6.5-7.5, is dried with ultrapure water eccentric cleaning at 60 DEG C
Fe-UFC presoma is obtained after the dry 12h of case.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment eight
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 6h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
PH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will precipitate
Object carries out eccentric cleaning, and 6500r/min for several times, until supernatant pH value is about 6.5-7.5, is dried with ultrapure water eccentric cleaning at 60 DEG C
Fe-UFC presoma is obtained after the dry 12h of case.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment nine
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 700 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment ten
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, and clear solution is formed under stirring, then plus
Entering suitable volumetric concentration is 37% formaldehyde, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate nine
Nitric hydrate iron (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution is in room
Temperature is lower to stand reaction 1.5h, and sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
PH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will precipitate
Object carries out eccentric cleaning, and 6500r/min for several times, until supernatant pH value is about 6.5-7.5, is dried with ultrapure water eccentric cleaning at 60 DEG C
Fe-UFC presoma is obtained after the dry 12h of case.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2h, heating rate in the tube-type atmosphere furnace under 900 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Embodiment 11
The present embodiment the following steps are included:
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, and clear solution is formed under stirring, then plus
Entering suitable volumetric concentration is 37% formaldehyde, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate nine
Nitric hydrate iron (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution is in room
Temperature is lower to stand reaction 1.5h, and sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
PH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will precipitate
Object carries out eccentric cleaning, and 6500r/min for several times, until supernatant pH value is about 6.5-7.5, is dried with ultrapure water eccentric cleaning at 60 DEG C
Fe-UFC presoma is obtained after the dry 12h of case.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 2.5h, heating speed in the tube-type atmosphere furnace under 1000 DEG C of argon gas
Rate is 1 DEG C/min, is cooled to room temperature and takes out product, obtains Fe-UFC composite material.
Embodiment 12
Step 1, the preparation of iron-containing Lauxite presoma；
The urea for weighing 92.7mmol is completely dissolved in 120mL ultrapure water, clear solution is formed under stirring, then
It is 37% formaldehyde that suitable volumetric concentration, which is added, makes the molar ratio 1:0.4 of urea and formaldehyde, after mixing evenly, is added appropriate
Fe(NO3)39H2O (Fe (NO3)3·9H2O), make solution ph 2, appropriate stirring is uniformly mixed solution.Then, solution exists
At room temperature stand reaction 1.5h, sediment is centrifuged, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant
Liquid pH value is 6.5-7.5,60 DEG C of dry 12h.Sample after drying is solidified into 48h in 2mol/L hydrochloric acid solution；Later, it will sink
Starch carry out eccentric cleaning, 6500r/min with ultrapure water eccentric cleaning for several times, until supernatant pH value is about 6.5-7.5, at 60 DEG C
Fe-UFC presoma is obtained after oven drying 12h.
Step 2, the preparation of iron-containing N doping Lauxite base carbon；
The resulting Fe-UFC presoma of step 1 is calcined into 3h, heating rate in the tube-type atmosphere furnace under 800 DEG C of argon gas
For 1 DEG C/min, it is cooled to room temperature and takes out product, obtain Fe-UFC composite material.
Claims (10)
1. a kind of preparation method of the adjustable iron-containing N doping Lauxite base carbon material in aperture, it is characterised in that: including with
Lower step:
(1) formalin is added in urea liquid, adds molysite after mixing evenly, until solution ph 2~4, obtains
To reaction solution, reaction solution reaction generates sediment, obtains Fe-UFC presoma after sediment is separated after post treatment；Wherein urinate
The molar ratio of element and formaldehyde is 1:(0.1~1.2)；
(2) Fe-UFC presoma is calcined to 2~3h under 700~1000 DEG C of protective atmospheres, obtains the adjustable iron-containing nitrogen in aperture
Adulterate Lauxite base carbon material.
2. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: in step (1), the volumetric concentration of the formalin used is 37%；Urea liquid is in every 120mL water
The urea that 92.7mmol is added is formulated.
3. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: molysite includes Fe(NO3)39H2O.
4. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: in step (1), reaction solution stands reaction 1h~6h at room temperature.
5. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: in step (1), separation is centrifuge separation；Post-processing is successively to be cleaned and dried, solidified and secondary clear
Wash drying.
6. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 5
Method, it is characterised in that: be cleaned and dried and secondary cleaning drying be by sediment undergoes washing to supernatant pH value be 6.5~7.5,
Then in 60 DEG C of dry 12h.
7. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 5
Method, it is characterised in that: solidification is that the sediment after drying is solidified 48h in 2mol/L hydrochloric acid solution.
8. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: calcining carries out in tube-type atmosphere furnace, and heating rate is 1 DEG C/min.
9. a kind of preparation side of the adjustable iron-containing N doping Lauxite base carbon material in aperture according to claim 1
Method, it is characterised in that: protective atmosphere is argon gas.
10. the adjustable iron-containing N doping ureaformaldehyde tree in aperture made from preparation method described in -9 any one according to claim 1
Aliphatic radical carbon material.
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