CN106622235B - For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion - Google Patents
For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 20
- 238000010891 electric arc Methods 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910002555 FeNi Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 23
- 229910052742 iron Inorganic materials 0.000 abstract description 22
- 239000000470 constituent Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000010405 anode material Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 229910002837 PtCo Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- -1 copper complex ion Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002669 PdNi Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/397—
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/347—Ionic or cathodic spraying; Electric discharge
Abstract
The present invention relates to for the graphene coated alloy nano catalyst and preparation method thereof by carbon dioxide conversion for carbon monoxide, the catalyst includes AxByAlloy nano particle and it is coated on the AxByThe graphene G or nonmetal doping graphene MG, described A, B on alloy nano particle surface are different metallic elements, and independently selected from Fe, Co, Ni, Cu, mass ratio x:y=(1~9) of the A and B: (9~1).Wherein AxByAlloy nano particle is active constituent, and the surface of graphene G described in the electron permeable of the alloy or MG layers of nonmetal doping graphene arrival catalyst enhance the electron density on surface, and then improves to reactant molecule CO2Absorption and activation, and improve the overall performance of catalyst.
Description
Technical field
The invention belongs to chemical catalyst technical fields, and in particular to for being the stone of carbon monoxide by carbon dioxide conversion
Black alkene clad alloy nanocatalyst and preparation method thereof.
Background technique
As abundant, nontoxic, reproducible carbon resource, CO2Gas can be widely used in producing hydro carbons, alcohols and formic acid etc.
High level chemicals.Currently, CO2Being chemically converted to CO is one of most important route, the highest attention by domestic and foreign scholars.It should
The realization of process is not only to alleviate the CO such as greenhouse effects, global warming, Ocean acidification2Negative effect effective way, and
Reaction product can be used as the primary raw material of famous chemical process F- T synthesis.The research and development of effective catalyst become CO2Chemical conversion
For the key of CO.
Currently, being used for CO2The catalyst for being chemically converted to CO reaction process mainly has photochemical catalyst, elctro-catalyst and heat to urge
Agent etc..Photochemical catalyst and elctro-catalyst efficiency are all very low, and preparation process is complicated, severe reaction conditions, reach industry far away
The requirement of production.In industrial processes, thermocatalyst is easier to prepare, strong operability.People are exerting always for many years
Power attempts to research and develop a variety of thermocatalysts applied to CO2Chemical conversion generates CO process.Mainly there is PtCo/ γ-Al at present2O3With
PdNi/CeO2(J.Catal.2013,301,30.)、Mo2C and Co-Mo2C(Angew.Chem.Int.Ed.2014,53,
6705.)、LaFe0.975Ir0.025O3(ACS Catal.2016,6,1172.), PtCo alloy nano particle are carried on TiO2、CeO2
Or ZrO2Catalyst such as (Angew.Chem.Int.Ed.2016,55,7968.), but reaction temperature all 300 DEG C or more, very
To reaching 1000 DEG C, and CO2Conversion ratio is not high (< 15%).The activity of catalyst can be greatly improved in spite of appropriate amount of hydrogen presence,
But it can lead to by-product CH4Generation, the selectivity of target product CO reduces.
Chinese patent CN 1724150A discloses title are as follows: CO2Decomposition catalyst and preparation method thereof.The technology utilizes
With Lacking oxygen, high-temperature stable composite conductor oxygen-permeating film material by infusion process load one of Pd, Cu, Ni, Fe, Pt or
Their alloy.Although selection of the catalyst that the weight metal content of preparation is 1~20% at 950 DEG C to target product CO
Property is up to 99% or more, but CO2Conversion ratio it is very low, be only 3% or so.
Chinese patent CN 103464134A discloses title are as follows: carbon dioxide decomposition prepare carbon monoxide catalyst and
Preparation method and application.The metal composite oxide Ce that the technology is doped cerium zirconium sosoloid using Mg, Ca0.8- xZr0.2MxO2-x(M=Mg, Ca), by the way that constantly circulation carries out CO in two-step reaction under normal pressure certain temperature constant interval2It decomposes
CO reaction is prepared, the catalyst thermal stability is good, the service life is long.But reaction temperature is very high, respectively 800~1100 DEG C and 1200
~1400 DEG C, and catalytic activity is lower.
Chinese patent CN 103933978A discloses title are as follows: a kind of support type for catalysis transform of carbon dioxide is received
Rice catalyst and its preparation method and application.The technology using ammoniacal copper complex ion be impregnated in carrier silica gel and iron content, cobalt, nickel, manganese,
Any one of zinc, palladium, barium, aluminium or two kinds of metals or its oxide are the carried copper base nano-catalyst of auxiliary agent.The catalysis
Agent is in 10~50vol.%CO2, 40~80vol.%H2, air speed be 5000~20000mL g-1h-1, temperature be 200~500 DEG C,
Pressure can synthesize CO co-production methanol under conditions of being 1~10MPa, but the selectivity of CO is lower, is no more than 60%.
Chinese patent CN 105293492A discloses title are as follows: a kind of to heat-treat CO using graphene-based catalyst2Synthesis
The method of CO.The technology prepares graphene oxide as precursor, using Hummers method using flaky graphite, and passes through chemistry
The method of stripping off prepares oxide such as WO3、ZnO、ZrO2、CeO2、MnO2、TiO2Any one of composite graphite alkene catalyst.There is water
In the presence of, which can be catalyzed CO at 25~90 DEG C of low temperature2Conversion forms CO, but activity is very low.
Chinese patent CN 105498780A discloses title are as follows: a kind of Cu/ZnO catalyst and preparation method thereof and in CO2
Application in chemical conversion.The active metal that mass ratio is 5~15% using microwave-assisted deposition-precipitation method by the technology
Cu is carried on flower-shaped or nano bar-shape ZnO carrier.The Cu/ZnO catalyst of preparation temperature be 250~270 DEG C, pressure 30
The CO that can be 1/3 by molar ratio in the fixed bed reactors of~45bar2/H2Gaseous mixture is converted into CO co-production methanol and methane,
But CO2Conversion ratio is lower and the selectivity of CO is not high.
In short, current all kinds of catalyzed conversion CO2Reaction temperature height, the energy consumption of reaction for synthesizing the catalyst needs of CO are high, living
Lower and CO the selectivity of property is not high.
Summary of the invention
It is complicated, anti-for preparation process present in the existing catalyst being used for by carbon dioxide conversion for carbon monoxide
The deficiencies of condition is harsh, low and CO the selectivity of activity is not high, stability is poor is answered, it is an object of the invention to provide one kind compared with low temperature
High activity, highly selective and high stability under degree and the catalyst and preparation method thereof with production application ability.
On the one hand, the present invention provides a kind of graphene coated alloy nano catalyst, which is characterized in that the catalyst
Include AxByAlloy nano particle and it is coated on the AxByThe graphene G or nonmetalloid on alloy nano particle surface mix
Miscellaneous graphene MG, described A, B are different metallic elements, and independently selected from Fe, Co, Ni, Cu, the mass ratio x of the A and B:
Y=(1~9): (9~1).
A in catalyst of the present inventionxByAlloy nano particle and graphene G or nonmetal doping graphene MG shape
At special core-shell structure.Wherein AxByAlloy nano particle is active constituent, graphene G described in the electron permeable of the alloy
Or the surface of MG layers of nonmetal doping graphene arrival catalyst, enhance the electron density on surface, and then improve to reaction
Object molecule CO2Absorption and activation, and improve the overall performance of catalyst.
Preferably, A in the catalystxByThe mass content of alloy nano particle is 60~95%.If the AxByAlloy
Nanoparticle content is lower to lead to active site deficiency, and high-content will lead to the imperfect of core-shell structure.
Preferably, nonmetalloid M is at least one of N, S, P, B in the nonmetal doping graphene MG,
The mass content of nonmetalloid M is 0.1~1% in the nonmetal doping graphene MG.
Preferably, the AxByThe particle size of alloy nano particle is 4~14nm.
Preferably, the graphene G or nonmetal doping graphene MG with a thickness of 0.2~2nm.
On the other hand, the present invention also provides a kind of preparation methods of graphene coated alloy nano catalyst, comprising:
A metal powder and B metal powder are filled in inside metal tube after evenly mixing according to mass ratio, and with the gold
Belong to pipe and forms anode；It is opposite with the anode level using graphite rod as cathode, containing methane or methane and impurity gas
Arc discharge is reacted 1~6 hour at 20~60A in the reaction cavity of mixed gas, is obtained the graphene coated alloy and is received
Rice catalyst.
Preferably, the material of the metal tube is A metal or B metal.
Preferably, the particle size of the A metal powder or/and B metal powder is 100~500 mesh.
Preferably, the arc discharge reaction before, reaction cavity is evacuated to 5~20Pa, then pass to methane,
Or the mixed gas of methane and impurity gas, the pressure of the mixed gas of the methane or methane and impurity gas is 0.05~
0.09MPa。
Preferably, the volume ratio of the methane and impurity gas is 9:1~1:9, the impurity gas is ammonia, vulcanization
At least one of hydrogen, hydrogen phosphide, diborane.
Preferably, the outer diameter of the metal tube is 6~10mm, internal diameter is 4~8mm, and length is 8~20cm.
Preferably, the diameter of the graphite rod is 6~10mm, length is 8~20cm.
Catalyst of the invention for by carbon dioxide conversion be reaction of carbon monoxide, under relatively mild conditions have compared with
High activity, carbon monoxide selective and thermal stability.Graphene coated alloy nano catalyst prepared by the present invention can be
High activity, highly selective and high stability under lower temperature and there is production application ability, and there is preparation method
Simply, controllably, it is at low cost the advantages that.In the presence of 200 DEG C, appropriate amount of hydrogen, air speed is 42000mL gcat -1h-1When, FeNi3@
NG is up to 99%, conversion ratio up to 20.2% to the selectivity that carbon dioxide conversion is carbon monoxide, and reaction 200h conversion ratio is still
It is maintained at 19% or more, the generating rate of carbon monoxide maintains 94mL min-1gcat -1。
Detailed description of the invention
Fig. 1 is FeNi3The transmission electron microscope photo of@G catalyst；
Fig. 2 is FeNi3The high resolution transmission electron microscopy photo of@NG catalyst；
Fig. 3 is FeNi3The performance of@NG catalyst continuous operation 200h.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention provides a kind of for the graphene coated alloy nano that carbon dioxide conversion is carbon monoxide to be catalyzed
Agent, the catalyst are represented by AxBy@G or AxBy@MG, wherein A, B Fe, Co, Ni, Cu metal, x=1~9, y=9~1,
G is graphene.Wherein active constituent is AxByAlloy nano particle, wherein metal (AxByAlloy nano particle) mass content
It can be 60~95%.The AxByThe particle size of alloy nano particle can be 4~14nm, can more preferably show catalytic effect.Institute
The thickness for stating graphene G or nonmetal doping graphene MG can be 0.2~2nm.
Above-mentioned AxByM in@MG can be nonmetallic for N, S, P, B etc..It is nonmetallic in the nonmetal doping graphene MG
The mass content of element M can be 0.1~1%, can more preferably promote the effect of catalyst.
The graphene coated alloy nano catalyst is prepared by easy one step of arc discharge method in the present invention.With
Under illustratively illustrate provided by the present invention for by carbon dioxide conversion be carbon monoxide graphene coated alloy nano urge
The preparation method of agent.
Be x:y=(1~9) according to mass ratio: A, B metal powder are uniformly mixed and are filled in metal tube by (9~1)
Portion, and anode is formed with the metal tube.The particle size of the A metal powder or/and B metal powder can be 100~500
Mesh.And the material selection A metal or B metal of the metal tube, it can further prevent urging described in the doping influence of foreign metal
The catalytic performance of agent.The metal pipe outside diameter 6~10mm, 4~8mm of internal diameter, 8~20cm of length.
Cathode (graphite rod) is fixed on the copper utensil of water cooling opposite with above-mentioned anode material level.The graphite rod
6~10mm of diameter, 8~20cm of length.
Before carrying out arc discharge reaction, it is 5~20Pa that reaction cavity, which is evacuated to pressure,.It is filled into reaction cavity
Entering reaction gas (mixed gas of methane or methane and impurity gas) to pressure is 0.05~0.09MPa.Wherein impurity gas
Selected from least one of ammonia, hydrogen sulfide, hydrogen phosphide, diborane.The volume ratio of the methane and impurity gas can for 9/1~
1/9。
Then anode and cathode is started into arc discharge reaction close to arc discharge and plasma is generated.It is wherein electric
Stream can be 20~60A, and the reaction time can be 1~6h.
Power supply is closed, by 2~6h of product natural subsidence obtained above, product is collected and obtains AxBy@G or AxBy@MG is urged
Agent.
The present invention prepares the catalytic performance test of catalyst.All catalysis reactions carry out in fixed bed reactors.
Catalyst fines are filled into the quartz ampoule of internal diameter 10mm, and are tightly attached to catalyst two sides so that catalyst becomes with silica wool
Round pie and the temperature control region for being placed in reactor.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas 200~
1~6h of pretreatment is carried out to catalyst at 400 DEG C, then passing to flow velocity is 50mL min-1CO2It is 10~100mL with flow velocity
min-15vol.%H2/ Ar mixed gas, reacts 5~10h at 150~300 DEG C, and product directly uses mass spectrograph and gas phase color
Spectrometer carries out qualitative and quantitative analysis.
The catalyst as made from the above method for temperature is 200~240 DEG C, can in the fixed bed reactors under normal pressure
A small amount of H will be contained2CO2It is converted into CO, shows higher activity, CO selectivity and stability, and there is preparation method letter
Easily, fast, it is low in cost the advantages that.In the presence of 200 DEG C, appropriate amount of hydrogen, air speed is 42000mL gcat -1h-1When, FeNi3@
NG is to CO2The selectivity for being converted into CO is up to 99%, conversion ratio up to 20.2%, reaction 200h conversion ratio be still maintained at 19% with
On, the generating rate of CO maintains 94mL min-1gcat -1.The present invention passes through inductively coupled plasma atomic emission spectrometry
The mass content for measuring alloy nano particle in the graphene coated alloy nano catalyst can be 60~95%.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
(particle size of Fe, Co metal powder is respectively 100 mesh, 300 to Fe, Co metal powder for being 5/3 by mass ratio
Mesh) composition anode inside the metal Fe pipe of outer diameter 10mm, internal diameter 5mm, length 16cm is uniformly mixed and is filled in, then by diameter
6mm, length 14cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
It is 0.05MPa that cavity, which is evacuated to and is re-filled with methane gas to pressure after pressure is 6Pa, then that anode and cathode is close to production
Raw arc discharge and plasma, and power supply is closed after reacting 2h under electric current is 20A, by reaction product natural subsidence 4h and receive
Collection obtains Fe5Co3@G catalyst；
Weigh a certain amount of Fe5Co3@G catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 4h to catalyst at 250 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 50mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 10h at 200 DEG C, the results are shown in Table 1.
Embodiment 2
(particle size of Fe, Cu metal powder is respectively 100 mesh, 400 to Fe, Cu metal powder for being 1/8 by mass ratio
Mesh) composition anode inside the Ni metal pipe of outer diameter 6mm, internal diameter 4mm, length 10cm is uniformly mixed and is filled in, then by diameter
10mm, length 18cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will be anti-
It answers cavity to be evacuated to be re-filled with mixed gas to the pressure of methane and ammonia that volume ratio is 6/1 after pressure is 20Pa and be
0.09MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 3h under electric current is 50A
Power supply is closed, by reaction product natural subsidence 3h and collection obtains FeCu8@NG catalyst；
Weigh a certain amount of FeCu8@NG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 1h to catalyst at 400 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 80mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 6h at 300 DEG C, the results are shown in Table 1.
Embodiment 3
Fe, Ni metal powder (particle size of Fe, Ni metal powder is 100 mesh, 200 mesh) for being 1/3 by mass ratio are equal
Even mixing is simultaneously filled in composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
The cathode graphite rod of degree 16cm is fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, and reaction cavity is taken out
Vacuum to pressure is re-filled with methane and ammonia that volume ratio is 3/1 mixed gas to pressure after being 10Pa is 0.06MPa, then
By anode and cathode close to extremely generation arc discharge and plasma, and power supply is closed after reacting 4h under electric current is 40A, it will be anti-
It answers product natural subsidence 5h and collects and obtain FeNi3@NG catalyst；
Weigh a certain amount of FeNi3@NG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 200 DEG C, the results are shown in Table 1.
Embodiment 4
(particle size of Ni, Co metal powder is respectively 200 mesh, 300 to Ni, Co metal powder for being 2/5 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 7mm, internal diameter 4mm, length 10cm is uniformly mixed and is filled in, then by diameter
6mm, length 14cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
It is 0.07MPa that cavity, which is evacuated to and is re-filled with methane gas to pressure after pressure is 6Pa, then that anode and cathode is close to production
Raw arc discharge and plasma, and power supply is closed after reacting 6h under electric current is 20A, by reaction product natural subsidence 6h and receive
Collection obtains Ni2Co5@G catalyst；
Weigh a certain amount of Ni2Co5@G catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 1h to catalyst at 320 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 80mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 5h at 250 DEG C, the results are shown in Table 1.
Embodiment 5
(particle size of Ni, Cu metal powder is respectively 200 mesh, 400 to Ni, Cu metal powder for being 1/6 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 10mm, internal diameter 8mm, length 16cm is uniformly mixed and is filled in, then by diameter
10mm, length 12cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will be anti-
It answers cavity to be evacuated to be re-filled with mixed gas to the pressure of methane and ammonia that volume ratio is 8/1 after pressure is 5Pa and be
0.08MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 3h under electric current is 50A
Power supply is closed, by reaction product natural subsidence 5h and collection obtains NiCu6@NG catalyst；
Weigh a certain amount of NiCu6@NG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 50mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 6h at 250 DEG C, the results are shown in Table 1.
Embodiment 6
(particle size of Co, Cu metal powder is respectively 300 mesh, 500 to Co, Cu metal powder for being 3/8 by mass ratio
Mesh) composition anode inside the Ni metal pipe of outer diameter 10mm, internal diameter 7mm, length 18cm is uniformly mixed and is filled in, then by diameter
10mm, length 18cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will be anti-
Answering cavity to be evacuated to, to be re-filled with methane gas to pressure after pressure is 7Pa be 0.05MPa, then by anode and cathode close to extremely
Arc discharge and plasma are generated, and closes power supply after reacting 6h under electric current is 20A, simultaneously by reaction product natural subsidence 6h
It collects and obtains Co3Cu8@G catalyst；
Weigh a certain amount of Co3Cu8@G catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 4h to catalyst at 250 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 10h at 200 DEG C, the results are shown in Table 1.
Embodiment 7
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 1/3 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 14cm is uniformly mixed and is filled in, then by diameter
8mm, length 16cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
Cavity, which is evacuated to, to be re-filled with mixed gas to the pressure of methane and hydrogen sulfide that volume ratio is 4/1 and is after pressure is 10Pa
0.06MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 4h under electric current is 40A
Power supply is closed, by reaction product natural subsidence 5h and collection obtains FeNi3@SG catalyst；
Weigh a certain amount of FeNi3@SG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 200 DEG C, the results are shown in Table 1.
Embodiment 8
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 1/3 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 14cm is uniformly mixed and is filled in, then by diameter
8mm, length 16cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
Cavity, which is evacuated to, to be re-filled with mixed gas to the pressure of methane and hydrogen phosphide that volume ratio is 5/1 and is after pressure is 10Pa
0.06MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 4h under electric current is 40A
Power supply is closed, by reaction product natural subsidence 5h and collection obtains FeNi3@PG catalyst；
Weigh a certain amount of FeNi3@PG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 200 DEG C, the results are shown in Table 1.
Embodiment 9
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 1/3 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 14cm is uniformly mixed and is filled in, then by diameter
8mm, length 16cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
Cavity, which is evacuated to, to be re-filled with mixed gas to the pressure of methane and diborane that volume ratio is 2/1 and is after pressure is 10Pa
0.06MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 4h under electric current is 40A
Power supply is closed, by reaction product natural subsidence 5h and collection obtains FeNi3@BG catalyst；
Weigh a certain amount of FeNi3@BG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 200 DEG C, the results are shown in Table 1.
Embodiment 10
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 1/3 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 14cm is uniformly mixed and is filled in, then by diameter
8mm, length 16cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
It is 0.06MPa that cavity, which is evacuated to and is re-filled with methane gas to pressure after pressure is 6Pa, then that anode and cathode is close to production
Raw arc discharge and plasma, and power supply is closed after reacting 5h under electric current is 30A, by reaction product natural subsidence 6h and receive
Collection obtains FeNi3@G catalyst；
Weigh a certain amount of FeNi3@G catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-1
5vol.%H2/ Ar gas carries out pretreatment 3h to catalyst at 340 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 100mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 300 DEG C, the results are shown in Table 1.
Embodiment 11
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 1/8 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 10mm, internal diameter 8mm, length 16cm is uniformly mixed and is filled in, then by diameter
8mm, length 18cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
Cavity, which is evacuated to, to be re-filled with mixed gas to the pressure of methane and ammonia that volume ratio is 3/1 and is after pressure is 10Pa
0.08MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 4h under electric current is 40A
Power supply is closed, by reaction product natural subsidence 5h and collection obtains FeNi8@NG catalyst；
Weigh a certain amount of FeNi8@NG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 8h at 200 DEG C, the results are shown in Table 1.
Embodiment 12
(particle size of Fe, Ni metal powder is respectively 400 mesh, 200 to Fe, Ni metal powder for being 6/1 by mass ratio
Mesh) composition anode inside the W metal pipe of outer diameter 8mm, internal diameter 6mm, length 16cm is uniformly mixed and is filled in, then by diameter
8mm, length 18cm cathode graphite rod be fixed on the copper utensil of water cooling and opposite with above-mentioned anode material level, will react
Cavity, which is evacuated to, to be re-filled with mixed gas to the pressure of methane and ammonia that volume ratio is 3/1 and is after pressure is 10Pa
0.08MPa, then by anode and cathode close to extremely generation arc discharge and plasma, and after reacting 3h under electric current is 50A
Power supply is closed, by reaction product natural subsidence 4h and collection obtains Fe6Ni@NG catalyst；
Weigh a certain amount of Fe6Ni@NG catalyst filling enters in fixed bed reactors.First being passed through flow velocity is 50mL min-15vol.%H2/ Ar gas carries out pretreatment 2h to catalyst at 300 DEG C, and then passing to flow velocity is 50mL min-1CO2
It is 20mL min with flow velocity-15vol.%H2/ Ar mixed gas, reacts 6h at 250 DEG C, the results are shown in Table 1.
Table 1 is the performance that catalyst is carbon monoxide in embodiment 1-12 to carbon dioxide conversiona
aReaction condition: 100mg catalyst (note: in addition to A in catalyst prepared by the present inventionxByThe matter of alloy nano particle
It is the mass content of nonmetalloid (graphene G or nonmetal doping graphene MG) except amount content.But it is described
The content that nonmetalloid M is adulterated in nonmetal doping graphene MG is less, only nonmetal doping graphene MG
0.1~1%, quantitative deviation is larger, then elocutionary meaning is little).
Fig. 1 FeNi3The transmission electron microscope photo of@G catalyst, the catalyst distribution is uniform as we know from the figure, and
FeNi3Particle diameter distribution is 4~11nm；
Fig. 2 FeNi3The high resolution transmission electron microscopy photo of@NG catalyst, as we know from the figure FeNi3Alloying pellet
Lattice be 0.21nm, correspond to (111) crystal face, the graphene G with a thickness of 0.4nm；
Fig. 3 FeNi3Performance (the reaction condition: 100mg FeNi of@NG catalyst continuous operation 200h3@NG,50mL min- 1CO2,20mL min-15vol.%H2/ Ar, 200 DEG C), the catalyst shows good stability as we know from the figure.
Claims (8)
1. a kind of graphene coated alloy nano catalyst, which is characterized in that the catalyst includes FeNi3Alloy nano particle,
And it is coated on the FeNi3The nonmetal doping graphene MG on alloy nano particle surface, the nonmetalloid are mixed
Nonmetalloid M is N in miscellaneous graphene MG, the mass content of nonmetalloid M in the nonmetal doping graphene MG
It is 0.1~1%, FeNi in the catalyst3The mass content of alloy nano particle is 60~95%.
2. graphene coated alloy nano catalyst according to claim 1, which is characterized in that the FeNi3Alloy nano
The particle size of particle is 4~14 nm.
3. graphene coated alloy nano catalyst according to claim 1 or 2, which is characterized in that the nonmetallic member
Plain doped graphene MG with a thickness of 0.2~2 nm.
4. a kind of preparation method of the graphene coated alloy nano catalyst as described in any one of claim 1-3, feature
It is, comprising:
Fe metal powder and Ni metal powder are filled in inside metal tube after evenly mixing according to mass ratio, and with the metal
Pipe forms anode；
It is opposite with the anode level using graphite rod as cathode, in the reaction chamber containing methane and the mixed gas of impurity gas
Arc discharge is reacted 1~6 hour at 20~60 A in body, obtains the graphene coated alloy nano catalyst.
5. the preparation method according to claim 4, which is characterized in that the Fe metal powder or/and Ni metal powder
Particle size is 100~500 mesh.
6. the preparation method according to claim 4, which is characterized in that before arc discharge reaction, by reaction chamber
Body is evacuated to 5~20 Pa, then passes to the mixed gas of methane and impurity gas, the mixing of the methane and impurity gas
The pressure of gas is 0.05~0.09 MPa.
7. the preparation method according to any one of claim 4-6, which is characterized in that the body of the methane and impurity gas
For product than being 9:1~1:9, the impurity gas is ammonia.
8. carbon dioxide conversion is being the application in carbon monoxide by a kind of graphene coated alloy nano catalyst, feature exists
In the graphene coated alloy nano catalyst includes FeNi3Alloy nano particle and it is coated on the FeNi3Alloy is received
Nonmetalloid M is in nonmetal doping the graphene MG, the nonmetal doping graphene MG on rice corpuscles surface
The mass content of nonmetalloid M is 0.1~1% in N, the nonmetal doping graphene MG, in the catalyst
FeNi3The mass content of alloy nano particle is 60~95%.
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