CN108493461A - A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles - Google Patents
A kind of N adulterates the catalyst and preparation method thereof of porous carbon coating Fe, Co bimetal nano particles Download PDFInfo
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Abstract
A kind of porous carbon coating Fe of N doping, the catalyst and preparation method thereof of Co bimetal nano particles belong to energy and material and electrochemical field.The catalyst with glucose be the sources C, g C3N4For the sources N and the sources C and template, FeCl3·6H2O and Co (NO3)2·6H2O is source metal, must plant the Fe Co NC catalyst that N adulterates porous carbon coating Fe, Co using high temperature step calcination legal system, catalyst is three-dimensional porous unordered stacked structure.Fe, Co are with Fe0.3Co0.7、Fe2O3, Co objects mutually exist, be uniformly wrapped on N doping porous carbon in.Compared with common Pt bases catalyst, ORR performances are not much different with commodity Pt/C catalysis in alkaline medium, and OER performances will be far above Pt/C catalyst, have higher stability and methanol tolerant performance.Compared with common bimetallic alloy catalyst, which has more active species, larger specific surface area.In addition, the catalyst low in raw material price and abundance, preparation process is simple, is conducive to large-scale production, has higher practical value.
Description
Technical field
The invention belongs to energy and material and electrochemical fields, are related to a kind of applied to fuel cell, electrolysis water and metal-sky
The oxygen reduction reaction in the fields such as pneumoelectric pond and the elctro-catalyst of oxygen evolution reaction and preparation method thereof.
Background technology
Fuel cell, metal-air battery, electrolysis water etc. are formed because of its convenient, pollution-free, dependable performance, energy density height
For the hot spot of new energy field research.However, the oxygen electrode reaction of these devices (refers specifically to oxygen reduction reaction (Oxygen herein
Reduction reaction, ORR) and oxygen evolution reaction (Oxygen evolution reaction, OER)) dynamic process
Slowly, overpotential is high, thus greatly hinders its commercialization process.Solve the problems, such as this key be to develop it is efficient, low at
This ORR and OER catalyst is to improve their working efficiency.Currently, Pt bases and Ru/Ir bases catalyst are catalysis ORR respectively
The best catalyst with OER performances, but can not be used as ORR and OER dual purpose catalysts, and precious metals pt, Ru, Ir
Reserves it is limited, expensive, stability is poor, also limit their large-scale application.Therefore exploitation high catalytic activity, height
Stability and low-cost bi-functional oxygen electrode catalyst have important scientific value and realistic meaning.
Transition metal-nitrogen-C catalyst because ORR activity is higher, performance is stable, cheap the advantages that due to be concerned,
However single metal-doped catalyst is difficult to have the bis- catalysis of excellent ORR and OER simultaneously at present.Bimetallic is even
More metal-loaded catalysis may theoretically provide various active site, it is possible to while meeting catalysis ORR and OER processes
It is required that and being used as double effect oxygen electrode catalyst.Document [Nano Research 2017,10,2332-2343] is with C3N4For
Carbon source and nitrogen source, Fe (acac)3And Co (acac)2The respectively sources Fe and the sources Co, by being made using pyrolysismethod after ball milling mixing
FeCo alloy is supported on the FeCo/NC catalyst of N doped graphene pieces.The experimental results showed that although the preparation of the catalyst
Method is simple, large specific surface area, stability are good, but its active material is single, ORR and OER catalytic performances need further to be carried
It is high.Document [Journal of Colloid and Interface Science 2018,514,656-663] is with melamine
For carbon nitrogen source, FeCl3·6H2O and CoCl2·6H2O is that source metal is successfully prepared CoFe alloy particle using a step pyrolysismethod
Part is coated on the catalyst (CoFe@NCNTs) in the carbon nanotube of N doping.Its tubular structure of the catalyst not only contributes to
Increase the active sites of catalyst, while being also beneficial to the progress of mass transfer, the catalyst stability of the tubular structure is superior in addition.
But its ORR performance and OER performances are poor, still need to further increase.
In conclusion although the catalyst of bimetal-doped has preferable ORR and OER stability, its activity is still not
Can meet the needs of practical application.Tracing it to its cause, to may be current preparation method cannot be such that the catalyst of bimetal-doped carries
Caused by enough active bit class.The method of substep containing transition metal will have even repeatedly forms active sites twice
Process, it is possible to improve " one-step preparation method " formation the insufficient present situation of active bit class, various active position structure can be formed
Type is to improve ORR the and OER performances of catalyst.
The present invention is with cheap FeCl3·6H2O and Co (NO3)2·6H2O is presoma, and glucose is carbon source, g-
C3N4For the source C, N and pore-creating template, porous carbon coating Fe, the Co bimetal nano grain of N doping is obtained using substep pyrolysismethod
The Fe-Co@NC catalyst of son is for being catalyzed ORR and OER reactions.
Invention content
In view of the problems of the existing technology, the present invention provides a kind of N doping porous carbon coating Fe, Co bimetal nano grain
The catalyst and preparation method thereof of son, which uses cheap glucose for the sources C, g-C3N4For the sources N, the sources C and mould
Plate, FeCl3·6H2O and Co (NO3)2·6H2O is source metal, is made using high temperature step calcination method.It is catalyzed with common Pt bases
Agent is compared, and ORR performances are worked as with commodity 20wt.%Pt/C catalytic phases in alkaline medium, and OER performances will be far above commodity
20wt.%Pt/C catalyst, and there is higher stability and methanol tolerant performance；In addition, low in raw material price and source is rich
Richness, preparation process is simple, is conducive to large-scale production, has higher practical value.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of N adulterates the Fe-Co NC catalyst of porous carbon coating Fe, Co bimetal nano particles, which is
Three-dimensional porous structure possesses larger specific surface area, can guarantee the mass transfer mistake of participation reactive material during catalysis ORR and OER
Journey；Fe, Co are with Fe0.3Co0.7、Fe2O3, simple substance Co objects mutually exist, be largely coated on N doping porous carbon in, and uniformly
Distribution, which can effectively avoid being in direct contact for metallic and electrolyte in reaction process, while inhibit metallic
Aggregation, improve the stability of catalyst；The incorporation of N atoms can manufacture a certain amount of defective bit and form pyridine nitrogen, pyrroles
Nitrogen and metal-N isoreactivity species, and the Fe coated0.3Co0.7、Fe2O3, Co particles can activate N doping carbon-coating, to
ORR and OER active site quantity has been significantly greatly increased, has improved the activity of catalyst.
A kind of N adulterates the preparation method of the Fe-Co NC catalyst of porous carbon coating Fe, Co bimetal nano particles, including
Following steps：
1) urea at a temperature of 400-600 DEG C is calcined into the product that 0.1-24h is obtained and is named as g-C3N4；From initial temperature
The heating rate that degree is warming up to calcination temperature is 3-10 DEG C of min-1。
2) water and ethyl alcohol are pressed 1:0.01-100 volume ratio mixing after obtain solution A, by above-mentioned steps 1) in product g-
C3N4、 FeCl3·6H2O, glucose is dissolved in solution A, is then heated to 40-100 DEG C, and reaction 0.1-48h obtains solution B,
In, a concentration of 0.01-1mol L of glucose in solution B-1.The glucose and FeCl3·6H2The molar ratio of O is 12:
1-100, glucose and g-C3N4Mass ratio be 10:0.1-100.
3) drying steps 2) obtained by solution B, be made catalyst precarsor 1..
4) under inert gas shielding, the calcining step 3 at a temperature of 400-1200 DEG C) in gained catalyst precarsor 1. 0.1-
48h.The heating rate that calcination temperature is warming up to from initial temperature is 1-10 DEG C of min-1.The inert gas is N2, Ar and N2/
It is one or more in Ar mixed gas.
5) water and ethyl alcohol are pressed 1:Solution C is obtained after the volume ratio mixing of 0.01-100, then by Co (NO3)2·6H2O and step
It is rapid 4) in products therefrom be placed in C solution and mix.Co (the NO3)2·6H2O and FeCl3·6H2The molar ratio of O is 5:
0.1-100。
6) drying steps 5) obtained by solution C, be made catalyst precarsor 2..
7) under inert gas shielding, the calcining step 6 at a temperature of 400-1200 DEG C) in gained catalyst precarsor 2. 0.1-
48h.The heating rate that calcination temperature is warming up to from initial temperature is 1-10 DEG C of min-1.The inert gas is N2, Ar and N2/
It is one or more in Ar mixed gas.
Co (the NO3)2·6H2O and FeCl3·6H2What O can be replaced the metals such as Mn, Fe, Co, Ni, Cu or Zn can
Any two in soluble and the above mixture.
The drying means in drying steps described in step 3) and step 6) is that vacuum drying oven is dry, air -oven is dry
Dry, stirring drying, freeze-drying etc., drying temperature is -40-500 DEG C, drying time 1-100h.
The Fe-Co NC catalyst that N of the present invention adulterates porous carbon coating Fe, Co bimetal nano particles is used as combustion
Expect ORR the and/or OER elctro-catalysts of the energy storages such as battery, metal-air battery and electrolysis water and conversion equipment.
Beneficial effects of the present invention：
1) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst is the sources C, g-C using glucose3N4For the sources N, the sources C and pore creating material, FeCl3·6H2O and Co (NO3)2·6H2O
It for source metal, is prepared using " substep pyrolysismethod ", the method for fractional steps can increase activated species, be conducive to be catalyzed simultaneously
ORR and OER reactions.
2) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst, Fe, Co nano-particle are most of to be uniformly wrapped in the porous carbon of N doping, and reaction process can be effectively avoided
Middle metallic and electrolyte are in direct contact, while inhibiting the aggregation of metallic, improve the stability of catalyst
3) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst, by regulating and controlling preparation condition, such as FeCl3·6H2O and Co (NO3)2·6H2The molar ratio of O, g-C3N4With glucose
The achievable catalyst such as mass ratio, calcination temperature, calcination time controllable preparation；
4) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst, specific surface area is larger, and poration process is simple, controllable, it is ensured that participates in reaction species during ORR and OER
Mass transport process；
5) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst is raw materials used cheap, derives from a wealth of sources, and helps to realize commercialized development；Moreover, preparation process is simple, warp
It helps, is safe, reproducible, being conducive to the amplification production of the catalyst；
6) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst, shows excellent ORR and OER catalytic performances in alkaline electrolyte, and Δ E is only that (Δ E is double work(to 0.84V
Energy catalyst performance evaluation parameter, Δ E is smaller, and double-function catalyzing performance is better), much smaller than Pt/C catalyst and current preparation
Only form single FeCo alloy nanoparticle catalyst.
7) N for using the method for the invention to prepare adulterates the Fe-Co of porous carbon coating Fe, Co bimetal nano particles
NC catalyst shows excellent methanol tolerance performance and ORR and OER catalytic stabilities in alkaline electrolyte.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 1.
Fig. 2 is that scanning electron microscope (SEM) photo of sample is made according to embodiment 1 under the conditions of 1 μm.
Fig. 3 is that transmission electron microscope (TEM) photo of sample is made according to embodiment 1 under the conditions of 100nm.
Fig. 4 (a) is nitrogen adsorption/desorption isothermal curve that sample is made according to embodiment 1；Fig. 4 (b) is root embodiment 1
The pore distribution curve of sample is made.
Fig. 5 (a) is that 20wt.%Pt/C catalyst is commercialized in O according to sample made from embodiment 1-4 and comparative example2It is full
0.1 mol L of sum-1ORR polarization curves in KOH electrolyte at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 5 (b) is that 20wt.%Pt/C catalyst is commercialized in O according to sample made from embodiment 1-4 and comparative example2It is full
0.1 mol L of sum-1OER polarization curves in KOH electrolyte at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 6 (a) is that 20wt.%Pt/C catalyst is commercialized in O according to sample made from embodiment 1,5,6 and comparative example2
The 0.1mol L of saturation-1ORR polarization curves in KOH electrolyte at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 6 (b) is that 20wt.%Pt/C catalyst is commercialized in O according to sample made from embodiment 1,5,6 and comparative example2
The 0.1mol L of saturation-1OER polarization curves in KOH electrolyte at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.
Fig. 7 is according to sample made from embodiment 1 in O2The 0.1mol L of saturation-1At room temperature linear in KOH electrolyte
Volt-ampere (LSV) curve is scanned, speed is swept：10mV s-1, rotating speed：400rpm, 900rpm, 1600rpm, 2500rpm.
Fig. 8 is Koutecky-Levich (K-L) curve corresponding with the LSV spectrograms of Fig. 7.
Fig. 9 (a) is according to sample made from embodiment 1 in O2The 0.1mol L of saturation-1Pass through at room temperature in KOH electrolyte
ORR polarization curves before and after 8000 circle accelerated ageing tests (CV scanning ranges -0.4-0.1V), sweep speed：10mV s-1, rotating speed：
1600 rpm.Fig. 9 (b) is according to sample made from embodiment 1 in O2The 0.1mol L of saturation-1It is passed through at room temperature in KOH electrolyte
The OER polarization curves before and after 2000 circle accelerated ageing tests (CV scanning range 0.4-0.8V) are crossed, speed is swept：10mV s-1, rotating speed：
1600rpm。
Figure 10 be embodiment 1 made from sample respectively at room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
3mol L-1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed：10mV s-1。
Figure 11 be comparative example be commercialized 20wt.%Pt/C catalyst respectively at room temperature, O2The 0.1mol L of saturation-1KOH
Electrolyte, O2The 3mol L of saturation-1CH3OH+0.1mol L-1CV figures in KOH electrolyte, sweep speed：10mV s-1。
Present invention test reference electrode used is the Ag/AgCl electrodes of KCl saturations.
Specific implementation mode
The present invention is explained in detail with reference to specific example, but the present invention is not limited only to these specific implementations
Example.
Embodiment 1：G-Fe-Co@NC-1:(G is glucose, Fe-Co@NC-1 to 1-900-800:1 refers to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 1:1 and FeCl is first added3·6H2O, 900 finger first time pyrolysis temperatures are
900 DEG C, 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 135mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 20mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming obtains target after natural cooling to 800 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-1:1-900-800.
Embodiment 2：G-Fe-Co@NC-2:(G is glucose, Fe-Co@NC-2 to 1-900-800:1 refers to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 2:1 and FeCl is first added3·6H2O, 900 finger first time pyrolysis temperatures are
900 DEG C, 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、250mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 135mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 20mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming obtains target after natural cooling to 800 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-2:1-900-800；
Embodiment 3：G-Fe-Co@NC-2:(G is glucose, Fe-Co@NC-2 to 3-900-800:3 refer to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 2:3 and FeCl is first added3·6H2O, 900 finger first time pyrolysis temperatures are
900 DEG C, 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 203mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 20mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming obtains target after natural cooling to 800 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-2:3-900-800；
Embodiment 4：G-Fe-Co@NC-2:(G is glucose, Fe-Co@NC-2 to 4-900-800:4 refer to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 2:4 and FeCl is first added3·6H2O, 900 finger first time pyrolysis temperatures are
900 DEG C, 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 270mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 20mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming obtains target after natural cooling to 800 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-2:4-900-800；
Embodiment 5：G-Co-Fe@NC-1:(G is glucose, Co-Fe@NC-1 to 1-900-800:1 refers to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 1:1 and Co (NO are first added3)2·6H2O, 900 refer to pyrolysis temperature for the first time
Degree is 900 DEG C, and 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、135mg Co
(NO3)2·6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will mix
It closes uniform solution B to be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..By catalyst
1. precursor is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming is forged to 900 DEG C
1h is burnt, Fe@NC-900 catalyst is obtained after natural cooling；Again by 125mg FeCl3·6H2O and obtain Fe@NC-900 catalyst
It is placed in 10mL deionizations and obtains solution C with stirring 2h in the mixed solution of 20mL ethyl alcohol；Uniformly mixed solution C is transferred to
In culture dish, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, grinding is uniform
It is placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming obtains mesh after natural cooling to 800 DEG C of calcining 30min
Mark catalyst G-Fe-Co@NC-1:1-900-800.
Embodiment 6：G-FeCo@NC-1:(G is glucose, FeCo@NC-1 to 1-900-800:1 refers to FeCl in raw material3·6H2O
With Co (NO3)2·6H2The molal weight ratio of O is 1:1 and FeCl is added simultaneously3·6H2O and Co (NO3)2·6H2O, 900 refer to the
Pyrolysis temperature is 900 DEG C, and 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O、 135mg Co(NO3)2·6H2O and 500mg glucose is dissolved in solution A, then heats 8h at 80 DEG C in oil bath pan
Solution B is obtained, uniformly mixed solution B is transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, before catalyst is made
Body is 1..1. catalyst precarsor is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Program
900 DEG C of calcining 1h are warming up to, Fe@NC-900 catalyst is obtained after natural cooling；The powder of calcining gained is again placed in quartz
In boat, 5 DEG C of min under nitrogen protection-1Temperature programming obtains final catalyst G- after natural cooling to 800 DEG C of calcining 30min
FeCo@NC-1:1-900-800。
Embodiment 7：(G is glucose to G-Fe@NC-900, and Fe refers to FeCl in raw material3·6H2O, 900 refer to pyrolysis temperature for the first time
Degree is 900 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Final catalyst Fe@NC-900 are obtained after natural cooling；
Embodiment 8：G-Fe-Co@NC-1:(G is glucose, Fe-Co@NC-1 to 1-600-600:1 refers to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 1:1 and FeCl is first added3·6H2O, 600 finger first time pyrolysis temperatures are
600 DEG C, 600 second of pyrolysis temperature of finger are 600 DEG C)
Urea is placed in tube furnace 3 DEG C of min under nitrogen protection-11h is calcined under temperature programming to 400 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 2h is then heated at 60 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 50 DEG C of vacuum drying chambers dry 48h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 3 DEG C of min-1Temperature programming to 600 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 135mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 20mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 50 DEG C of air drying cabinets dry 48h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under nitrogen protection 3 DEG C of min-1Temperature programming obtains target after natural cooling to 600 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-1:1-600-600.
Embodiment 9：G-Fe-Co@NC-1:(G is glucose, Fe-Co@NC-1 to 1-1100-1100:1 refers in raw material
FeCl3·6H2O and Co (NO3)2·6H2The molal weight ratio of O is 1:1 and FeCl is first added3·6H2O, 1100 refer to heat for the first time
It is 1100 DEG C to solve temperature, and 1,100 second of pyrolysis temperature of finger are 1100 DEG C)
Urea is placed in tube furnace 10 DEG C of min under nitrogen protection-16h is calcined under temperature programming to 600 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 10ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 12h is then heated at 100 DEG C in oil bath pan obtains solution B, and mixing is equal
Even solution B is transferred in culture dish, and 300 DEG C of air drying cabinets dry 3h, and catalyst precarsor is made 1..By catalyst precarsor
1. being placed in mortar, grinding is uniformly placed in quartz boat, under nitrogen protection 10 DEG C of min-1Temperature programming to 1100 DEG C calcine
6h obtains Fe@NC-900 catalyst after natural cooling；Again by 135mg Co (NO3)2·6H2O and obtain Fe@NC-900 catalysis
Agent is placed in 10mL deionizations and obtains solution C with stirring 2h in the mixed solution of 20mL ethyl alcohol；Uniformly mixed solution C is shifted
Into culture dish, 300 DEG C of air drying cabinets dry 3h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, grinding is equal
It is even to be placed in quartz boat, 10 DEG C of min under nitrogen protection-1Temperature programming obtains mesh after natural cooling to 1100 DEG C of calcining 6h
Mark catalyst G-Fe-Co@NC-1:1-1100-1100.
Embodiment 10：G-Fe-Co@NC-1:(G is glucose, Fe-Co@NC-1 to 1-900-800:1 refers to FeCl in raw material3·
6H2O and Co (NO3)2·6H2The molal weight ratio of O is 1:1 and FeCl is first added3·6H2O, 900 finger first time pyrolysis temperatures are
900 DEG C, 800 second of pyrolysis temperature of finger are 800 DEG C)
Urea is placed in tube furnace 5 DEG C of min under nitrogen protection-14h is calcined under temperature programming to 550 DEG C of calcination temperatures
Obtain g-C3N4；20ml water and 50ml ethyl alcohol are obtained into solution A after mixing, take 100mg g-C3N4、125mg FeCl3·
6H2O and 500mg glucose is dissolved in solution A, and 8h is then heated at 80 DEG C in oil bath pan obtains solution B, will be uniformly mixed
Solution B be transferred in culture dish, 80 DEG C of air drying cabinets dry 10h, and catalyst precarsor is made 1..1. by catalyst precarsor
It is placed in mortar, grinding is uniformly placed in quartz boat, under protection of argon gas 5 DEG C of min-1Temperature programming to 900 DEG C calcining 1 h,
Fe@NC-900 catalyst is obtained after natural cooling；Again by 135mg Co (NO3)2·6H2It O and obtains Fe@NC-900 catalyst and sets
Stirring 2h obtains solution C in the mixed solution of 10mL deionizations and 50mL ethyl alcohol；Uniformly mixed solution C is transferred to training
It supports in ware, 80 DEG C of air drying cabinets dry 10h, obtain catalyst precarsor 2.；2. precursor is placed in mortar, after grinding uniformly
It is placed in quartz boat, under protection of argon gas 5 DEG C of min-1Temperature programming obtains target after natural cooling to 800 DEG C of calcining 30min
Catalyst G-Fe-Co@NC-1:1-900-800.
Comparative example 1：20wt.%Pt/C catalyst (Alfa Aesar) is commercialized).
Fig. 1 is according to sample X-ray diffraction (XRD) spectrogram made from embodiment 1.By the JCPDS cards point of XRD spectra
Metal species in 1 sample of embodiment known to analysis contain three kinds of crystalline structures：Return in two characteristic peaks of 45.0 °, 65.7 ° appearance
Belong to Fe0.3Co0.7(JCPDS 48-1818), in 44.2 °, 51.5 °, 75.9 ° of characteristic peaks for Co nano particles occur
(JCPDS 89-7093) belongs to Fe at the peak of 29.8 °, 47.6 °, 52.0 ° appearance2O3Nano particle.In addition, attached at 26.5 °
It is close that there are one (002) faces (JCPDS 20-0258) that peak belongs to graphitic carbon；Show that carbon material has good carbonization structure.
Fig. 2 is scanning electron microscope (SEM) photo that sample is made according to embodiment 1.Embodiment 1 is made as can be seen from Figure 2
Sample in a large amount of metallic be coated in carbon shell and be evenly distributed on the three-dimensional porous carbon of unordered accumulation, except this it
Outside, also a small amount of exposed nano-particle is distributed in catalyst surface.The carbon structure of this unordered accumulation can be improved effectively
The porosity of catalyst and specific surface area etc..
Fig. 3 is transmission electron microscope (TEM) photo that sample is made according to embodiment 1.Found out by what Fig. 3 can be more clear, it is real
Applying sample made from example 1 has a large amount of metallic to be coated in carbon shell and is evenly distributed on porous carbon, metal particle size
About in 20-50nm.This clad structure can avoid being in direct contact for metallic and electrolyte solution, improve the steady of material
It is qualitative.
Fig. 4 (a) is nitrogen adsorption/desorption isothermal curve that sample is made according to embodiment 1.Embodiment 1 as we know from the figure
Sample obtained is in P/P0To show hysteresis loop (IV types adsorption curve) within the scope of 0.4-1, illustrate that there are meso-hole structure, meters
The specific surface area of catalyst known to calculating is up to 403m2g-1.Sample well made from embodiment 1 known to Fig. 4 (b) pore size distribution curves
Diameter is distributed in 3.5 nm.Larger specific surface area and abundant pore structure contribute to mass transfer and the more active sites of exposure, to
Improve ORR and OER performances.
Fig. 5 (a) is according to sample made from embodiment 1-4 and comparative example 1 in O2The 0.1mol L of saturation-1KOH electrolyte
In ORR polarization curves at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.Fig. 5 (b) is according to made from embodiment 1-4
Sample is with comparative example 1 in O2The 0.1mol L of saturation-1OER polarization curves in KOH electrolyte at room temperature, sweep speed：10mV s-1,
Rotating speed：1600rpm.By Fig. 5 (a) and Fig. 5 (b) it is found that the ratio of two kinds of metallic atoms is to the Electrochemical Performances of catalyst
It is larger.The atomic ratio of Fe and Co is 2:1, ORR take-off potential is best；The atomic ratio of Fe and Co is 1:1, OER performance is best.From
The difunctional angles of ORR and OER consider that the atomic ratio of Fe and Co are 1:The minimum 0.84V of 1, Δ E, ORR and OER best performances
(usually with OER in j=10mA cm-2With ORR in j=-3.0mA cm-2Between potential difference Δ E weigh elctro-catalyst
Difunctional electrocatalysis characteristic, Δ E is smaller, and difunctional electrocatalysis characteristic is better).
Fig. 6 (a) is according to sample and comparative example 1 made from embodiment 1,5,6 and 7 in O2The 0.1mol L of saturation-1KOH
ORR polarization curves in electrolyte at room temperature, sweep speed：10mV s-1, rotating speed：1600rpm.Fig. 6 (b) be according to embodiment 1,5,
Sample made from 6 and 7 is with comparative example 1 in O2The 0.1mol L of saturation-1OER polarization curves in KOH electrolyte at room temperature, sweep
Speed：10mV s-1, rotating speed：1600rpm.According to sample ORR performance ratios made from embodiment 1 according to sample made from embodiment 5
And it is more preferable according to sample made from embodiment 6, but slightly below sample made from embodiment 7, illustrate to apply sample made from example 1 and 7
Show superior ORR activity.It applies the E of sample made from example 1 compared with business Pt/C1/2Only, explanation lower 10mV than Pt/C
It is the ORR catalyst for having preferable foreground to apply sample made from example 1.In addition, the OER curves shown from Fig. 6 (b) can know implementation
Sample OER performances made from example 1 are best.It can be seen that it is most to apply sample (Δ E=0.84V) made from example 1 by calculating Δ E
Superior bifunctional catalyst.
Fig. 7 is according to sample made from embodiment 1 in O2The 0.1mol L of saturation-1At room temperature linear in KOH electrolyte
Volt-ampere (LSV) curve is scanned, speed is swept：10mV s-1, rotating speed：400rpm、900rpm、1600rpm、2500rpm.It can by Fig. 7
Know, with the increase of electrode rotating speed, sample ORR take-off potentials made from embodiment 1 remain unchanged, but limiting diffusion current is close
Degree constantly increases.
Fig. 8 is that Koutecky-Levich (K-L) curve that the LSV curves (Fig. 9) of sample obtain is made according to embodiment 1.
The electron transfer number that 1 surface catalysis ORR of embodiment is calculated according to K-L equations is 4.08, illustrates that sample made from embodiment 1 is urged
It participates in reacting with 4 electronic processes when changing ORR.
Fig. 9 (a) is according to sample made from embodiment 1 in O2The 0.1moL L of saturation-18000 circles are carried out in KOH electrolyte
The ORR polarization curve comparison diagrams after (- 0.4~0.1V of CV scanning ranges) are tested in accelerated ageing, sweep speed：10mV s-1, rotating speed：
1600 rpm；Fig. 9 (b) is sample O made from embodiment 12The 0.1moL L of saturation-12000 circles are carried out in KOH electrolyte to accelerate
OER curve comparison figures after burn-in test (0.4~0.8V of CV scanning ranges), sweep speed：10mV s-1, rotating speed：1600rpm.By
For Fig. 9 (a) it is found that catalyst made from embodiment 1 is after 8000 circle cycles, CV curves show embodiment 1 without significant change
Catalyst ORR stability obtained is preferable.By Fig. 9 (b) it is found that catalyst made from embodiment 1 is after 2000 circle cycles,
OER curves are in 10mA cm-2When corresponding current potential only shuffle 5mV, show also have during catalyst OER made from embodiment 1
There is significant stability.
Figure 10 is sample made from embodiment 1 respectively in N2Saturation and O2The 0.1M KOH solutions and O of saturation2The 0.1 of saturation
M KOH+3M CH3CV curves are carried out in OH solution, sweep speed：10mV s-1.As shown in Figure 10, catalyst made from embodiment 1 exists
3M CH are added in electrolyte3Before and after OH, the CV curves of Fe-Co@NC catalyst do not have significant change, show that embodiment 1 is made
Catalyst influenced by methanol fuel smaller, may be used as methanol fuel cell cathode catalyst.
Figure 11 is comparative example 1 respectively in N2Saturation and O2The 0.1M KOH solutions and O of saturation2The 0.1M KOH+3 M of saturation
CH3CV curves are carried out in OH solution, sweep speed：10mV s-1.As shown in Figure 11, commercialization 20wt.%Pt/C catalyst is being added
3M CH3The apparent methanol oxidation peak detected in -0.5 to 0.2V potential range after OH, shows 1 methanol tolerance of comparative example
Performance is poor.
Embodiments of the present invention above described embodiment only expresses, but therefore can not be interpreted as special to the present invention
The limitation of the range of profit, it is noted that for those skilled in the art, without departing from the inventive concept of the premise,
Various modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of N adulterates the Fe-Co NC catalyst of porous carbon coating Fe, Co bimetal nano particles, which is characterized in that described
Catalyst use glucose for the sources C, g-C3N4For the sources N, the sources C and template, FeCl3·6H2O and Co (NO3)2·6H2O is metal
Source is made using high temperature step calcination method；Catalyst morphology is three-dimensional porous structure, and large specific surface area can ensure to participate in anti-
Answer the mass transport process of species；Fe, Co are with Fe0.3Co0.7、Fe2O3, simple substance Co objects mutually exist, be largely coated on N doping it is more
It in the carbon of hole, and is uniformly distributed, is capable of providing various active species, improve catalyst activity；The catalyst structure can have simultaneously
Effect avoids being in direct contact for metallic and electrolyte in reaction process, and inhibits the aggregation of metallic, improves catalyst
Stability.
2. a kind of N described in claim 1 adulterates the Fe-Co NC catalyst of porous carbon coating Fe, Co bimetal nano particles
Preparation method, it is characterised in that following steps：
1) urea under 400-600 DEG C of calcination temperature is calcined into the product that 0.1-24h is obtained and is named as g-C3N4；
2) solution A is obtained after mixing water with ethyl alcohol, by above-mentioned steps 1) in product g-C3N4、FeCl3·6H2O, glucose dissolves
In solution A, it is heated to 40-100 DEG C, reaction 0.1-48h obtains solution B, wherein a concentration of 0.01- of glucose in solution B
1mol L-1；The glucose and FeCl3·6H2The molar ratio of O is 12:1-100, glucose and g-C3N4Mass ratio be
10:0.1-100；
3) drying steps 2) obtained by solution B, be made catalyst precarsor 1.；
4) under inert gas shielding, calcining step 3) in gained catalyst precarsor 1.；
5) solution C is obtained after mixing water with ethyl alcohol, then by Co (NO3)2·6H2Products therefrom is placed in C solution in O and step 4)
Middle mixing；Co (the NO3)2·6H2O and FeCl3·6H2The molar ratio of O is 5:0.1-100；
6) drying steps 5) obtained by solution C, be made catalyst precarsor 2.；
7) under inert gas shielding, calcining step 6) in gained catalyst precarsor 2. obtain Fe-Co@NC catalyst.
3. a kind of N according to claim 2 adulterates the preparation method of the Fe-Co NC catalyst of porous carbon coating Fe, Co,
It is characterized in that, Co (the NO3)2·6H2O and FeCl3·6H2What O can be replaced Mn, Fe, Co, Ni, Cu or Zn metal can
Any two in soluble and the above mixture.
4. a kind of N according to claim 2 or 3 adulterates the preparation side of the Fe-Co NC catalyst of porous carbon coating Fe, Co
Method, which is characterized in that the calcination temperature in step 4) and step 7) is 400-1200 DEG C, calcination time 0.1-48h.
5. a kind of N according to claim 2 or 3 adulterates the preparation side of the Fe-Co NC catalyst of porous carbon coating Fe, Co
Method, which is characterized in that the volume ratio of water and ethyl alcohol described in step 2) is 1:0.01-100；Water described in step 5) and second
The volume ratio of alcohol is 1:0.01-100.
6. a kind of N according to claim 4 adulterates the preparation method of the Fe-Co NC catalyst of porous carbon coating Fe, Co,
It is characterized in that, the volume ratio of the water and ethyl alcohol described in step 2) is 1:0.01-100；Water described in step 5) and ethyl alcohol
Volume ratio be 1:0.01-100.
7. a kind of N according to Claims 2 or 3 or 6 adulterates the preparation of the Fe-Co NC catalyst of porous carbon coating Fe, Co
Method, which is characterized in that the drying means in drying steps described in step 3) and step 5) is vacuum drying oven drying, air
Oven drying, stirring are dry, frozen drying one or more, and drying temperature is -40-500 DEG C, drying time 1-
100h。
8. a kind of N according to claim 5 adulterates the preparation method of the Fe-Co NC catalyst of porous carbon coating Fe, Co,
It is characterized in that, the drying means in drying steps described in step 3) and step 5) is that vacuum drying oven is dry, air -oven
Drying, stirring are dry, frozen drying one or more, and drying temperature is -40-500 DEG C, drying time 1-100h.
9. a kind of N according to Claims 2 or 3 or 6 or 8 adulterates the Fe-Co NC catalyst of porous carbon coating Fe, Co
Preparation method, which is characterized in that be warming up to the heating rate of calcination temperature in step 1), step 4), step 7) from initial temperature
For 1-10 DEG C of min-1。
10. a kind of N according to claim 7 adulterates the preparation method of the Fe-Co NC catalyst of porous carbon coating Fe, Co,
It is characterized in that, in step 1), step 4), step 7) from room temperature to the heating rate of calcination temperature be 1-10 DEG C of min-1。
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