CN109382125A - A kind of nitrogen co-doped carbon-based elctro-catalyst of nickel, preparation method and application - Google Patents
A kind of nitrogen co-doped carbon-based elctro-catalyst of nickel, preparation method and application Download PDFInfo
- Publication number
- CN109382125A CN109382125A CN201710651278.9A CN201710651278A CN109382125A CN 109382125 A CN109382125 A CN 109382125A CN 201710651278 A CN201710651278 A CN 201710651278A CN 109382125 A CN109382125 A CN 109382125A
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- nitrogen
- elctro
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 17
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008103 glucose Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001354 calcination Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 7
- 239000003708 ampul Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Abstract
The present invention provides a kind of preparation methods of the nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps: A) nickel salt, dicyandiamide and ammonium chloride are dispersed in water, it is calcined after dry；B hydro-thermal reaction is carried out after) mixing calcined product in water with glucose；C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.The present invention is reacted using confinement, and the nickel of monatomic form is dispersed in the carbon-based material of N doping, the reunion and loss of active site are avoided.Obtained catalyst shows excellent electro-catalysis carbon dioxide reduction performance, to the selectivity of carbon monoxide up to 99%.Preparation method provided by the invention has the characteristics that process flow is simple, low in cost, yield is suitable for greatly industrial production, has potential application.The present invention also provides a kind of nitrogen co-doped carbon-based elctro-catalyst of nickel and its applications.
Description
Technical field
The invention belongs to catalysis technical field more particularly to a kind of nitrogen co-doped carbon-based elctro-catalysts of nickel, preparation method
And its application.
Background technique
The energy is the basis of human society survival and development.The energy of necessary for human depends critically upon petroleum-based energy at present.
Energy crisis is not only exacerbated to consuming excessively for petroleum-based energy, also causes generated carbon dioxide excess emissions, brings
The greenhouse effects being on the rise seriously threaten the survival and development of the mankind.It can not only be effective to the trans-utilization of carbon dioxide
Reduce atmosphere in carbon dioxide accumulation, moreover it is possible to by carbon dioxide conversion at contain carbon chemicals, to promote the circulation of carbon.
The side that the realization carbon dioxide conversion that reduction is current most prospect utilizes is carried out to carbon dioxide by electro-catalysis
One of formula.Although achieving many progress for carbon dioxide electro-catalysis reduction, the diversity of reduzate makes dioxy
It is low to change carbon reduction selectivity, especially water is restored to hydrogen as the main competitive reaction in carbon dioxide catalytic reduction process,
It is low so as to cause carbon dioxide conversion.Noble metal such as Au, Ag are applied to show excellent choosing when carbon dioxide reduction
Selecting property, but its expensive price still limits the further development as carbon dioxide reduction elctro-catalyst.Therefore it finds
The carbon dioxide reduction elctro-catalyst of Cheap highly effective becomes urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of nitrogen co-doped carbon-based elctro-catalyst of nickel, preparation method and application, this hairs
The reaction selectivity of the nitrogen co-doped carbon-based elctro-catalyst of nickel in bright is high, and low in cost.
The present invention provides a kind of preparation method of nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps:
A nickel salt, dicyandiamide and ammonium chloride are dispersed in water), calcined after dry；
B hydro-thermal reaction is carried out after) mixing calcined product in water with glucose；
C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Preferably, the nickel salt is bivalent soluble nickel salt.
Preferably, the mass ratio of the nickel salt and dicyandiamide is (0.2~5): 100；
The mass ratio of the nickel salt and ammonium chloride is (0.2~5): 500.
Preferably, the step A) in calcine temperature be 500~650 DEG C；
The step A) in calcine time be 1~4 hour.
Preferably, the step A) in the mass ratio of calcined product and glucose be (0.7~1.5): 5.
Preferably, the temperature of the hydro-thermal reaction is 160~200 DEG C；
The time of the hydro-thermal reaction is 10~20 hours.
Preferably, the step C) in calcine temperature be 800~1100 DEG C；
The step C) in calcine time be 0.5~4 hour.
The present invention provides a kind of nitrogen co-doped carbon-based elctro-catalyst of nickel, is made according to above-mentioned preparation method.
Preferably, the mass fraction of nitrogen is 3~6% in the nitrogen co-doped carbon-based elctro-catalyst of the nickel；
The mass fraction of nickel is 1~3% in the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Application of the nitrogen co-doped carbon-based elctro-catalyst of nickel described above in reduction carbon dioxide reaction
The present invention provides a kind of preparation methods of the nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps: A) by nickel
Salt, dicyandiamide and ammonium chloride disperse in water, are calcined after dry；B) calcined product is mixed in water with glucose
After carry out hydro-thermal reaction；C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.Benefit of the invention
It is reacted with confinement, the nickel of monatomic form is dispersed in the carbon-based material of N doping, avoid reunion and the stream of active site
It loses.Obtained catalyst shows excellent electro-catalysis carbon dioxide reduction performance, reachable to the selectivity of carbon monoxide
99%.With process flow, simple, low in cost, yield is suitable for greatly the spies such as industrial production to preparation method provided by the invention
Point, has potential application.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the X-ray diffraction pattern of product in the embodiment of the present invention 1；
Fig. 2 is the TEM figure of product in the embodiment of the present invention 1；
Fig. 3 is the distribution diagram of element of product in the embodiment of the present invention 1；
Fig. 4 is the X-ray photoelectron spectroscopic analysis figure of product in the embodiment of the present invention 1；
Fig. 5 is the HAADF figure of product in the embodiment of the present invention 1；
Fig. 6 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 1；
Fig. 7 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 2；
Fig. 8 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 3；
Fig. 9 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 4；
Figure 10 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 5；
Figure 11 is the linear voltammetric scan figure of the elctro-catalyst in comparative example 1 of the present invention；
Figure 12 is the linear voltammetric scan figure of the elctro-catalyst in comparative example 2 of the present invention；
Figure 13 is that the catalyst in the embodiment of the present invention 1, comparative example 1 and comparative example 2 aoxidizes carbon dioxide reduction at one
The faradic efficiency curve of carbon.
Specific embodiment
The present invention provides a kind of preparation methods of the nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps:
A nickel salt, dicyandiamide and ammonium chloride are dispersed in water), calcined after dry；
B hydro-thermal reaction is carried out after) mixing calcined product in water with glucose；
C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Elctro-catalyst reaction selectivity made from preparation method in the present invention is high, and at low cost.
The present invention disperses nickel salt, dicyandiamide and ammonium chloride in water, then evaporating water after stirring at 80 DEG C is forged
It burns, obtains calcined product.In the present invention, the nickel salt is preferably bivalent soluble nickel salt, more preferably nickel nitrate, second
Sour nickel, nickel chloride；The mass ratio of the nickel salt and dicyandiamide is preferably (0.2~5): 100, more preferably (1~4): 100；Institute
The mass ratio for stating nickel salt and ammonium chloride is (0.2~5): 500, more preferably (1~4): 500.Specifically, in implementation of the invention
In example, 1:100:500,3.5:100:500 or 4.7:100:500 can be.In the present invention, the temperature calcined for the first time is excellent
It is selected as 500~650 DEG C, more preferably 550~600 DEG C；The time calcined for the first time is preferably 1~4 hour, more preferably 2
~3 hours.The present invention is preferably heated up with the rate of 5~10 DEG C/min, is calcined, has been calcined after being warming up to calcination temperature
Temperature fall after finishing.
The product calcined for the first time and glucose carry out hydro-thermal reaction after mixing in water, described calcined for the first time
The mass ratio of product and glucose is preferably (0.7~1.5): 5, more preferably (1~1.2): the temperature of 5. hydro-thermal reactions
Preferably 160~200 DEG C, more preferably 180~190 DEG C；The time of the hydro-thermal reaction is preferably 10~20 hours, more preferably
It is 12~18 hours.To its natural cooling after the completion of hydro-thermal reaction, then by the product of hydro-thermal reaction successively use deionized water and
Ethyl alcohol is cleaned, and is then dried.
The product of hydro-thermal reaction is calcined, the calcining preferably carries out under argon atmosphere, the temperature of the calcining
Preferably 800~1100 DEG C, more preferably 900~1000 DEG C；The time of the calcining is preferably 0.5~4 hour, more preferably
1~3 hour.The present invention is preferably warming up to the calcination temperature with the rate of 5~10 DEG C/min, is then calcined, and has calcined
Room temperature is cooled to the rate of 5~10 DEG C/min after finishing, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
The present invention also provides a kind of nitrogen co-doped carbon-based elctro-catalysts of nickel, are made according to above-mentioned preparation method.The present invention
In the nitrogen co-doped carbon-based elctro-catalyst of nickel in the mass fraction of nitrogen be preferably 3~6%, more preferably 4%, the mass fraction of nickel
Preferably 1~3%, more preferably 1.4%.N element has two kinds of forms of graphite nitrogen and pyridine nitrogen, Ni and pyridine nitrogen in the catalyst
It is connected.Catalyst outermost layer be enclosed with Glucose Carbon metaplasia at graphene.
The present invention also provides application of the above-mentioned elctro-catalyst in catalysis reduction carbon dioxide reaction.
The present invention provides a kind of preparation methods of the nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps: A) by nickel
Salt, dicyandiamide and ammonium chloride disperse in water, are calcined after dry；B) calcined product is mixed in water with glucose
After carry out hydro-thermal reaction；C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.Benefit of the invention
It is reacted with confinement, the nickel of monatomic form is dispersed in the carbon-based material of N doping, while introducing glucose protective layer the most,
Avoid the reunion and loss of active site in high-temperature burning process.Obtained catalyst shows excellent electro-catalysis dioxy
Change carbon reducing property, to the selectivity of carbon monoxide up to 99%.Preparation method provided by the invention have process flow it is simple,
Low in cost, yield is suitable for greatly the features such as industrial production, has potential application.
In order to further illustrate the present invention, with reference to embodiments to a kind of nitrogen co-doped carbon-based electricity of nickel provided by the invention
Catalyst, preparation method and application are described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
Nickel chloride, dicyandiamide, ammonium chloride 3.5:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 500 DEG C calcine 1 hour, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 12 is small at 180 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, with the heating rate of 5 DEG C/min in 1000 DEG C of argon atmospheres
Calcining 0.5 hour, is then down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
It is analyzed using sample of the XRD to preparation, the result is shown in Figure 1.Fig. 1 is the X-ray of product in the embodiment of the present invention 1
Diffraction pattern.As shown in Figure 1, the spectrogram of Fig. 1 and the spectrogram of graphene are consistent, it is possible to determine that the carbon of sample becomes through high-temperature process
Graphene.Ni is because content is few, there is no crystallizing in graphene, so being not in the diffraction maximum of Ni in spectrogram.
Tem analysis is carried out to the sample of preparation, as a result sees Fig. 2~3.Fig. 2 is the TEM figure of product in the embodiment of the present invention 1；
Fig. 3 is the distribution diagram of element of product in the embodiment of the present invention 1.As shown in Figure 2, prepared sample is sheet-like morphology, the member of Fig. 3
Plain distribution map shows that nickel and nitrogen are evenly distributed on carbon.
X-ray photoelectron spectroscopic analysis is carried out to the sample of preparation, as a result sees that Fig. 4, Fig. 4 are to produce in the embodiment of the present invention 1
The X-ray photoelectron spectroscopic analysis figure of product.Wherein figure a is the XPS map of Ni2p, and figure b is the XPS map of N1s, as shown in Figure 4 N
It is successfully mixed in carbon with Ni.
HAADF characterization is carried out to the sample of preparation, as a result sees that Fig. 5, Fig. 5 are the HAADF of product in the embodiment of the present invention 1
Figure.As shown in Figure 5, Ni is with single atomic dispersion in carbon substrate.
Embodiment 2
Nickel chloride, dicyandiamide, ammonium chloride 1:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 550 DEG C calcine 2 hours, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 12 is small at 180 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, with the heating rate of 5 DEG C/min in 1000 DEG C of argon atmospheres
Calcining 1 hour, is then down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Embodiment 3
Nickel chloride, dicyandiamide, ammonium chloride 4.7:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 600 DEG C calcine 3 hours, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 16 is small at 160 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, with the heating rate of 5 DEG C/min in 1000 DEG C of argon atmospheres
Calcining 3 hours, is then down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Embodiment 4
Nickel chloride, dicyandiamide, ammonium chloride 3.5:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 500 DEG C calcine 1 hour, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 12 is small at 180 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, with the heating rate of 5 DEG C/min in 1100 DEG C of argon atmospheres
Calcining 0.5 hour, is then down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Embodiment 5
Nickel chloride, dicyandiamide, ammonium chloride 3.5:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 500 DEG C calcine 1 hour, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 12 is small at 180 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, is forged in 800 DEG C of argon atmospheres with the heating rate of 5 DEG C/min
It burns 0.5 hour, room temperature is then down to the rate of temperature fall of 5 DEG C/min, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
Comparative example 1
Dicyandiamide, ammonium chloride 2:10 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, is evaporated；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 500 DEG C calcine 1 hour, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is mixed with mass ratio 1:5 with water with glucose, then hydro-thermal reaction 12 is small at 180 DEG C
When, obtained product is successively cleaned with deionized water and ethyl alcohol, is then dried；
Sample after hydro-thermal process is placed in quartz ampoule, with the heating rate of 5 DEG C/min in 1000 DEG C of argon atmospheres
Calcining 0.5 hour, is then down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains the carbon-based elctro-catalyst of N doping.
Comparative example 2
Nickel chloride, dicyandiamide, ammonium chloride 3.5:100:500 in mass ratio and water are mixed into dispersion, 80 DEG C stirred below, steams
It is dry；
The sample being evaporated is put into crucible, with the heating rate of 5 DEG C/min 500 DEG C calcine 1 hour, then with 5 DEG C/
The rate of temperature fall of min is down to room temperature；
Calcined sample is placed in quartz ampoule, is calcined in 1000 DEG C of argon atmospheres with the heating rate of 5 DEG C/min
0.5 hour, room temperature is then down to the rate of temperature fall of 5 DEG C/min, obtains carbon-based elctro-catalyst.
The elctro-catalyst that the present invention has detected Examples 1 to 5 and comparative example 1~2 obtains to the reduction activation of carbon dioxide,
As a result as figures 6 to 12 show, Fig. 6 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 1；Fig. 7 is the present invention
The linear voltammetric scan figure of elctro-catalyst in embodiment 2；Fig. 8 is the linear volt-ampere of the elctro-catalyst in the embodiment of the present invention 3
Scanning figure；Fig. 9 is the linear voltammetric scan figure of the elctro-catalyst in the embodiment of the present invention 4；Figure 10 is in the embodiment of the present invention 5
The linear voltammetric scan figure of elctro-catalyst；Figure 11 is the linear voltammetric scan figure of the elctro-catalyst in comparative example 1 of the present invention；Figure 12
For the linear voltammetric scan figure of the elctro-catalyst in comparative example 2 of the present invention；This hair it can be seen from above-mentioned linear voltammetric scan figure
Catalyst in bright Examples 1 to 5 is active with good carbon dioxide reduction, and the catalyst in comparative example 1 and comparative example 2
Reduction activation is poor.
The present invention tests the faradic efficiency for the elctro-catalyst that embodiment 1, comparative example 1 and comparative example 2 obtain, as a result such as
Shown in Figure 13, Figure 13 is that the catalyst in the embodiment of the present invention 1, comparative example 1 and comparative example 2 aoxidizes carbon dioxide reduction at one
The faradic efficiency curve of carbon.As seen from Figure 13, the nitrogen co-doped carbon-based elctro-catalyst of nickel in the embodiment of the present invention 1 has
Higher faradic efficiency is up to 99% to the selectivity of carbon dioxide reduction reaction, and urging in comparative example 1 and comparative example 2
The faradic efficiency highest of agent is less than 70%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the nitrogen co-doped carbon-based elctro-catalyst of nickel, comprising the following steps:
A nickel salt, dicyandiamide and ammonium chloride are dispersed in water), calcined after dry；
B hydro-thermal reaction is carried out after) mixing calcined product in water with glucose；
C) product of hydro-thermal reaction is calcined, obtains the nitrogen co-doped carbon-based elctro-catalyst of nickel.
2. preparation method according to claim 1, which is characterized in that the nickel salt is bivalent soluble nickel salt.
3. preparation method according to claim 1, which is characterized in that the mass ratio of the nickel salt and dicyandiamide be (0.2~
5): 100；
The mass ratio of the nickel salt and ammonium chloride is (0.2~5): 500.
4. preparation method according to claim 1, which is characterized in that the step A) in calcine temperature be 500~650
℃；
The step A) in calcine time be 1~4 hour.
5. preparation method according to claim 1, which is characterized in that the step A) in calcined product and glucose
Mass ratio be (0.7~1.5): 5.
6. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 160~200 DEG C；
The time of the hydro-thermal reaction is 10~20 hours.
7. preparation method according to claim 1, which is characterized in that the step C) in calcine temperature be 800~
1100℃；
The step C) in calcine time be 0.5~4 hour.
8. a kind of nitrogen co-doped carbon-based elctro-catalyst of nickel is made according to preparation method described in claim 1~7 any one.
9. the nitrogen co-doped carbon-based elctro-catalyst of nickel according to claim 8, which is characterized in that the nickel is nitrogen co-doped carbon-based
The mass fraction of nitrogen is 3~6% in elctro-catalyst；
The mass fraction of nickel is 1~3% in the nitrogen co-doped carbon-based elctro-catalyst of nickel.
10. the nitrogen co-doped carbon-based elctro-catalyst of nickel made from preparation method described in claim 1~7 any one or right are wanted
Application of the nitrogen co-doped carbon-based elctro-catalyst of nickel described in asking 8 or 9 in reduction carbon dioxide reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710651278.9A CN109382125B (en) | 2017-08-02 | 2017-08-02 | Nickel-nitrogen co-doped carbon-based electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710651278.9A CN109382125B (en) | 2017-08-02 | 2017-08-02 | Nickel-nitrogen co-doped carbon-based electrocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109382125A true CN109382125A (en) | 2019-02-26 |
| CN109382125B CN109382125B (en) | 2020-06-26 |
Family
ID=65412301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710651278.9A Active CN109382125B (en) | 2017-08-02 | 2017-08-02 | Nickel-nitrogen co-doped carbon-based electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109382125B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110142056A (en) * | 2019-05-09 | 2019-08-20 | 中国科学院化学研究所 | A method of metal-nitrogen-doped carbon catalysis material is prepared using metal ion liquid |
| CN111215099A (en) * | 2020-02-24 | 2020-06-02 | 中国科学技术大学 | MoSe2/Co9S8Nano heterostructure material and preparation method and application thereof |
| CN113548700A (en) * | 2021-07-26 | 2021-10-26 | 河南师范大学 | Preparation method of iron-nickel-nitrogen-carbon nano material |
| CN113707894A (en) * | 2021-08-20 | 2021-11-26 | 中国第一汽车股份有限公司 | Fuel cell catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111681A1 (en) * | 2006-04-18 | 2009-04-30 | Universita Degli Studi Di Padova | Electrocatalysts Based on Mono/Plurimetallic Carbon Nitrides for Fuel Cells Fueled with Hydrogen |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN105271217A (en) * | 2015-12-10 | 2016-01-27 | 湖南师范大学 | Method for preparing nitrogen-doped three-dimensional graphene |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN106423242A (en) * | 2016-09-12 | 2017-02-22 | 天津工业大学 | Preparation method of nitrogen-doped nickel/carbon high-performance ethanol oxidation catalyst |
| CN106513029A (en) * | 2016-12-06 | 2017-03-22 | 武汉工程大学 | Preparation method for metal nanoparticle-loaded nitrogen-doped porous graphene |
| CN106684396A (en) * | 2016-12-21 | 2017-05-17 | 北京化工大学 | Method for preparing bifunctional catalyst from peanut hull |
-
2017
- 2017-08-02 CN CN201710651278.9A patent/CN109382125B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111681A1 (en) * | 2006-04-18 | 2009-04-30 | Universita Degli Studi Di Padova | Electrocatalysts Based on Mono/Plurimetallic Carbon Nitrides for Fuel Cells Fueled with Hydrogen |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN105271217A (en) * | 2015-12-10 | 2016-01-27 | 湖南师范大学 | Method for preparing nitrogen-doped three-dimensional graphene |
| CN106423242A (en) * | 2016-09-12 | 2017-02-22 | 天津工业大学 | Preparation method of nitrogen-doped nickel/carbon high-performance ethanol oxidation catalyst |
| CN106513029A (en) * | 2016-12-06 | 2017-03-22 | 武汉工程大学 | Preparation method for metal nanoparticle-loaded nitrogen-doped porous graphene |
| CN106684396A (en) * | 2016-12-21 | 2017-05-17 | 北京化工大学 | Method for preparing bifunctional catalyst from peanut hull |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110142056A (en) * | 2019-05-09 | 2019-08-20 | 中国科学院化学研究所 | A method of metal-nitrogen-doped carbon catalysis material is prepared using metal ion liquid |
| CN111215099A (en) * | 2020-02-24 | 2020-06-02 | 中国科学技术大学 | MoSe2/Co9S8Nano heterostructure material and preparation method and application thereof |
| CN111215099B (en) * | 2020-02-24 | 2022-07-15 | 中国科学技术大学 | MoSe2/Co9S8Nano heterostructure material and preparation method and application thereof |
| CN113548700A (en) * | 2021-07-26 | 2021-10-26 | 河南师范大学 | Preparation method of iron-nickel-nitrogen-carbon nano material |
| CN113707894A (en) * | 2021-08-20 | 2021-11-26 | 中国第一汽车股份有限公司 | Fuel cell catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109382125B (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109382125A (en) | A kind of nitrogen co-doped carbon-based elctro-catalyst of nickel, preparation method and application | |
| CN109289888B (en) | Preparation method of boron-doped porous carbon nitride material | |
| Pai et al. | Preparation and characterization of porous Nb2O5 photocatalysts with CuO, NiO and Pt cocatalyst for hydrogen production by light-induced water splitting | |
| CN107661772B (en) | A kind of Nonmetal oxygen reduction catalyst and the preparation method and application thereof | |
| CN108598505B (en) | Preparation method of vanadium carbide/carbon cloth composite material and product | |
| CN113385185A (en) | High-activity and selective perovskite type photo-thermal catalyst and preparation method and application thereof | |
| CN104709932A (en) | Gamma-aluminium oxide nanometer material and preparation method of nickel/gamma-aluminium oxide catalyst | |
| CN103506146A (en) | Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof | |
| CN114588912B (en) | Preparation method and application of alkali metal doped perovskite catalyst suitable for methane dry reforming | |
| CN110127635B (en) | Graphite-phase carbon nitride and preparation method thereof, hydrogen production photocatalyst and application thereof | |
| CN109616669A (en) | Nanometer cobalt/nitrogen-doped carbon nanometer pipe composite material preparation method and applications | |
| CN104190461A (en) | Preparation method of CLSTON catalyst for catalyzing visual light to decompose water to prepare hydrogen | |
| CN104190460A (en) | Preparation method of CLMTON catalyst for catalyzing visual light to decompose water to prepare hydrogen | |
| CN113908833A (en) | Reverse water gas shift catalyst and preparation method and application thereof | |
| CN110420656B (en) | Gas-phase acidified g-C3N4 nanosheet and preparation method thereof | |
| CN110193374B (en) | Boron-carbon-nitrogen electrocatalytic material, preparation method thereof and application thereof in ammonia synthesis by nitrogen reduction | |
| CN107413340B (en) | A kind of methane water reformation hydrogen production catalyst and preparation method thereof | |
| CN108654628A (en) | A kind of Ni-Ce-Zr composite oxides/gamma-alumina catalyst and preparation method thereof | |
| CN110227533B (en) | Preparation method of graphite-phase carbon nitride photocatalyst | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN106140169B (en) | A kind of dimethyl ether-steam reforming hydrogen manufacturing structural catalyst and its preparation method and application | |
| CN115029716A (en) | Ni/Cu adjacent site double-metal monoatomic coordination nitrogen-rich carbon matrix electrocatalyst and preparation method and application thereof | |
| CN106311264B (en) | A kind of silicon dioxide carried nickel tungsten catalyst and the preparation method and application thereof | |
| Machin et al. | Catalytic combustion of methane on La-, Ce-, and Co-based mixed oxides | |
| CN114192180A (en) | Modified boron nitride loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |