CN106622235A - Graphene coated alloy nano catalyst for converting carbon dioxide into carbon monoxide and preparation method thereof - Google Patents
Graphene coated alloy nano catalyst for converting carbon dioxide into carbon monoxide and preparation method thereof Download PDFInfo
- Publication number
- CN106622235A CN106622235A CN201611104335.3A CN201611104335A CN106622235A CN 106622235 A CN106622235 A CN 106622235A CN 201611104335 A CN201611104335 A CN 201611104335A CN 106622235 A CN106622235 A CN 106622235A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alloy nano
- graphene
- methane
- 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
- 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 49
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 43
- 229910045601 alloy 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 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 70
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims description 67
- 239000007789 gas Substances 0.000 claims description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 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
- 239000002245 particle Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 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 28
- 239000000428 dust Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000010405 anode material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- 229910002837 PtCo Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent 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
- 238000009826 distribution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000012827 research and development 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 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
- 230000007812 deficiency Effects 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
- 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
- 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
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 invention relates to a graphene coated alloy nano catalyst for converting carbon dioxide into carbon monoxide and a preparation method thereof. The catalyst comprises AxBy alloy nano particles and graphene (G)/nonmetal element doped graphene (MG), which coats the surface of the AxBy alloy nano particles; wherein A and B individually represent different metal elements (Fe, Co, Ni, and Cu), and the mass ratio (x:y) of A to B is (1-9):(9-1). The AxBy alloy nano particles are the active component of the catalyst. The electrons of the alloy can penetrate the graphene (G)/nonmetal element doped graphene (MG) layer and reach the surface of the catalyst, thus the surface electron density is enhanced, the reactant (CO2) molecules can be better adsorbed and activated, and the overall performance of the catalyst is improved.
Description
Technical field
The invention belongs to chemical catalyst technical field, and in particular to for by carbon dioxide conversion for carbon monoxide stone
Black alkene clad alloy nanocatalyst and preparation method thereof.
Background technology
As abundant, nontoxic, reproducible carbon resource, CO2Gas can be widely used in producing hydro carbons, alcohols and formic acid etc.
High level chemicals.At present, CO2It is one of most important route to be chemically converted to CO, is paid high attention to by Chinese scholars.Should
The realization of process, is not only the CO such as alleviation greenhouse effects, global warming, Ocean acidification2Negative effect effective way, and
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.
It is presently used for CO2Being chemically converted to the catalyst of CO courses of reaction 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 complexity, severe reaction conditions, and industry is reached far away
The requirement of production.In industrial processes, thermocatalyst is easier to prepare, workable.For many years people are exerting always
Power attempts the various thermocatalysts of research and development and is applied to CO2Chemical conversion generates CO processes.Mainly there are 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 particles are carried on TiO2、CeO2
Or ZrO2(Angew.Chem.Int.Ed.2016,55,7968.) catalyst such as, but reaction temperature all more than 300 DEG C, very
To reaching 1000 DEG C, and CO2Conversion ratio it is not high (<15%).Existing despite appropriate amount of hydrogen can greatly improve the activity of catalyst,
But accessory substance CH can be caused4Generation, the selectivity of target product CO reduces.
Chinese patent CN 1724150A disclose entitled：CO2Decomposition catalyst and preparation method thereof.The technology is utilized
With Lacking oxygen, high-temperature stable composite conductor oxygen-permeating film material by infusion process load Pd, Cu, Ni, Fe, Pt in one kind or
Their alloy.Although prepare weight metal content be 1～20% catalyst at 950 DEG C to the selection of target product CO
Property is up to more than 99%, but CO2Conversion ratio it is very low, be only 3% or so.
Chinese patent CN 103464134A disclose entitled：Carbon dioxide decomposition prepare the catalyst of carbon monoxide and
Preparation method and application.The technology is doped the metal composite oxide Ce for obtaining using Mg, Ca to cerium zirconium sosoloid0.8- xZr0.2MxO2-x(M=Mg, Ca), by the way that constantly circulation carries out CO in two-step reaction at ambient pressure uniform temperature constant interval2Decompose
CO reactions are prepared, the catalyst heat endurance is good, life-span length.But reaction temperature is very high, respectively 800～1100 DEG C and 1200
～1400 DEG C, and catalysis activity is relatively low.
Chinese patent CN 103933978A disclose entitled：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 impregnated in carrier silica gel and iron content, cobalt, nickel, manganese,
Any one or two kinds of metals or its oxide in zinc, palladium, barium, aluminium 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 is can to synthesize CO co-production methyl alcohol under conditions of 1～10MPa, but the selectivity of CO it is relatively low, less than 60%.
Chinese patent CN 105293492A disclose entitled：One kind utilizes graphene-based catalyst thermal reduction CO2Synthesis
The method of CO.The technology prepares graphene oxide with flaky graphite as precursor, using Hummers methods, and by 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, the catalyst can be catalyzed CO at 25～90 DEG C of low temperature2Conversion forms CO, but activity is very low.
Chinese patent CN 105498780A disclose entitled：A kind of Cu/ZnO catalyst and preparation method thereof and in CO2
Application in chemical conversion.The technology is using the deposition-precipitation method of microwave radiation technology by active metal that mass ratio is 5～15%
Cu is carried on flower-shaped or nano bar-shape ZnO carriers.The Cu/ZnO catalyst of preparation temperature be 250～270 DEG C, pressure be 30
Can be by CO that mol ratio is 1/3 in the fixed bed reactors of～45bar2/H2Gaseous mixture is converted into CO co-productions methyl alcohol and methane,
But CO2Conversion ratio is relatively low and selectivity of CO is not high.
In a word, current all kinds of catalyzed conversion CO2The reaction temperature height of the catalyst needs of synthesis CO, energy consumption of reaction are high, living
Relatively low and CO the selectivity of property is not high.
The content of the invention
For existing complicated, anti-for the preparation process by carbon dioxide conversion existing for the catalyst of carbon monoxide
The deficiencies such as condition is harsh, low and CO the selectivity of activity is not high, stability is poor are answered, it is an object of the invention to provide one kind is compared with low temperature
High activity, high selectivity and high stability and the catalyst with production application ability and preparation method thereof under degree.
On the one hand, the invention provides a kind of graphene coated alloy nano catalyst, it is characterised in that the catalyst
Comprising AxByAlloy nano particle and it is coated on the AxByThe Graphene G on alloy nano particle surface or nonmetalloid are mixed
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 shapes
Into special core shell structure.Wherein AxByAlloy nano particle is active constituent, Graphene G described in the electron permeable of the alloy
Or nonmetal doping Graphene MG layers reach the surface of catalyst, strengthen the electron density on surface, and then improve to reaction
Thing molecule CO2Absorption and activation, and improve the overall performance of catalyst.
It is preferred that A in the catalystxByThe mass content of alloy nano particle is 60～95%.If the AxByAlloy
Nanoparticle content is relatively low to cause active site not enough, and high-load can cause the imperfect of core shell structure.
It is preferred that nonmetalloid M is at least one in 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.
It is preferred that the AxByThe particle size of alloy nano particle is 4～14nm.
It is preferred that the thickness of the Graphene G or nonmetal doping Graphene MG is 0.2～2nm.
On the other hand, present invention also offers a kind of preparation method of graphene coated alloy nano catalyst, including：
Be filled in inside metal tube after A metal dusts and B metal dusts are uniformly mixed according to mass ratio, and with the metal tube
Composition anode；Using graphite rod as negative electrode and the anode level of relative, in the mixing containing methane or methane and impurity gas
Arc discharge reacts 1～6 hour under 20～60A in the reaction cavity of gas, obtains the graphene coated alloy nano and urges
Agent.
It is preferred that the material of the metal tube is A metals or B metals.
It is preferred that the particle size of the A metal dusts or/and B metal dusts is 100～500 mesh.
It is preferred that the arc discharge react before, reaction cavity is evacuated to into 5～20Pa, then pass to methane,
Or the pressure of the mixed gas of the mixed gas of methane and impurity gas, the methane or methane and impurity gas be 0.05～
0.09MPa。
It is preferred that the volume ratio of the methane and impurity gas is 9:1～1:9, the impurity gas is ammonia, sulfuration
At least one in hydrogen, hydrogen phosphide, diborane.
It is preferred that the external diameter of the metal tube is 6～10mm, internal diameter is 4～8mm, and length is 8～20cm.
It is preferred that a diameter of 6～10mm of the graphite rod, length is 8～20cm.
The present invention catalyst for by carbon dioxide conversion be reaction of carbon monoxide, under relatively mild conditions with compared with
High activity, carbon monoxide selective and heat endurance.Graphene coated alloy nano catalyst prepared by the present invention can be
High activity, high selectivity and high stability under lower temperature and with production application ability, and with preparation method
Simply, controllable, low cost and other advantages.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 carbon dioxide conversion for the selectivity of carbon monoxide, and reaction 200h conversion ratios are still
More than 19% is maintained at, the generating rate of carbon monoxide maintains 94mL min-1gcat -1。
Description of the drawings
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 FeNi3@NG catalyst continuously runs the performance of 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, and the unrestricted present invention.
The invention provides a kind of graphene coated alloy nano for by carbon dioxide conversion for carbon monoxide is catalyzed
Agent, the catalyst is represented by AxBy@G or AxBy@MG, wherein A, B be 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
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 lift the effect of catalyst.
The present invention prepares the graphene coated alloy nano catalyst by the step of easy arc discharge method one.With
Under exemplarily illustrate provided by the present invention for carbon dioxide conversion is urged for the graphene coated alloy nano of carbon monoxide
The preparation method of agent.
It is x according to mass ratio：Y=(1～9):(9～1), A, B metal dust is uniformly mixed and is filled in metal tube
Portion, and constitute anode with the metal tube.The particle size of the A metal dusts or/and B metal dusts can be 100～500
Mesh.And the material selection A metals or B metals of the metal tube, can further prevent foreign metal doping affect described in urge
The catalytic performance of agent.6～10mm of the metal tube external diameter, 4～8mm of internal diameter, 8～20cm of length.
Negative electrode (graphite rod) is fixed on the copper utensil of water-cooled and above-mentioned anode material level of relative.The graphite rod
6～10mm of diameter, 8～20cm of length.
Before arc discharge reaction is carried out, reaction cavity is evacuated to into pressure for 5～20Pa.Fill in reaction cavity
It is 0.05～0.09MPa to enter reacting gas (mixed gas of methane or methane and impurity gas) to pressure.Wherein impurity gas
At least one in ammonia, hydrogen sulfide, hydrogen phosphide, diborane.The volume ratio of the methane and impurity gas can for 9/1～
1/9。
Then anode and negative electrode are close to arc discharge and plasma is produced, start arc discharge reaction.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 is obtained AxBy@G or AxBy@MG are urged
Agent.
The present invention prepares the catalytic performance test of catalyst.All of catalytic reaction is carried out in fixed bed reactors.
Catalyst fines is filled in the quartz ampoule of internal diameter 10mm, and is close to catalyst both sides with silica wool so that catalyst becomes
Round pie and it is placed in the temperature control region of reactor.Flow velocity is first passed through for 50mL min-15vol.%H2/ Ar gases 200～
1～6h of pretreatment is carried out to catalyst at 400 DEG C, flow velocity is then passed to for 50mL min-1CO2It is 10～100mL with flow velocity
min-15vol.%H2/ Ar mixed gas, react 5～10h at 150～300 DEG C, and product is directly with mass spectrograph and gas phase color
Spectrometer carries out qualitative and quantitative analysis.
By catalyst obtained in said method for temperature be 200～240 DEG C, can in the fixed bed reactors under normal pressure
Will be containing a small amount of H2CO2CO is converted into, higher activity, CO selectivity and stability is shown, and with preparation method letter
Easily, quick, with low cost the advantages of.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 ratios be still maintained at 19% with
On, the generating rate of CO maintains 94mL min-1gcat -1.The present invention passes through ICP-AES
The mass content for measuring alloy nano particle in the graphene coated alloy nano catalyst can be 60～95%.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that 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 the concrete numerical value of hereafter example.
Embodiment 1：
By Fe, Co metal dust (particle size of Fe, Co metal dust is respectively 100 mesh, 300 mesh) that mass ratio is 5/3
Even mixing is simultaneously filled in the metal Fe pipes inside composition anode of external diameter 10mm, internal diameter 5mm, length 16cm, then by diameter 6mm,
The negative electrode graphite rod of length 14cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, by reaction cavity
It is 0.05MPa that pressure is evacuated to be re-filled with methane gas to pressure after 6Pa, is then close on anode and negative electrode electric to producing
Arc discharge and plasma, and electric current be 20A under react 2h after close power supply, by product natural subsidence 4h and collection be
Obtain Fe5Co3@G catalyst；
Weigh a certain amount of Fe5Co3@G catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 4h at 250 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 50mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 10h is reacted, and the results are shown in Table 1.
Embodiment 2
By Fe, Cu metal dust (particle size of Fe, Cu metal dust is respectively 100 mesh, 400 mesh) that mass ratio is 1/8
Even mixing is simultaneously filled in the Ni metal pipe inside composition anode of external diameter 6mm, internal diameter 4mm, length 10cm, then by diameter 10mm,
The negative electrode graphite rod of length 18cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, by reaction cavity
Mixed gas to the pressure that pressure is evacuated to be re-filled with methane that volume ratio is 6/1 and ammonia after 20Pa is 0.09MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 3h in the case where electric current is 50A, will
Product natural subsidence 3h and collection obtain FeCu8@NG catalyst；
Weigh a certain amount of FeCu8@NG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 1h at 400 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 80mL min-15vol.%H2/ Ar mixed gas, at 300 DEG C 6h is reacted, and the results are shown in Table 1.
Embodiment 3
Fe, Ni metal dust (particle size of Fe, Ni metal dust is 100 mesh, 200 mesh) that mass ratio is 1/3 is uniformly mixed
Merging is filled in the W metal pipe inside composition anode of external diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
The negative electrode graphite rod of 16cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out very
Empty is that mixed gas to the pressure of methane that volume ratio is 3/1 and ammonia is re-filled with after 10Pa is 0.06MPa to pressure, then will
Anode and negative electrode are close to generation arc discharge and plasma, and close power supply after reacting 4h in the case where electric current is 40A, will be reacted
Product natural subsidence 5h and collection obtain FeNi3@NG catalyst；
Weigh a certain amount of FeNi3@NG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 4
By Ni, Co metal dust (particle size of Ni, Co metal dust is respectively 200 mesh, 300 mesh) that mass ratio is 2/5
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 7mm, internal diameter 4mm, length 10cm, then by diameter 6mm, length
Degree 14cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum is 0.07MPa to be re-filled with methane gas to pressure after 6Pa to pressure, and then anode and negative electrode are close to generation electric arc
Electric discharge and plasma, and electric current be 20A under react 6h after close power supply, by product natural subsidence 6h and collection obtain final product
To Ni2Co5@G catalyst；
Weigh a certain amount of Ni2Co5@G catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 1h at 320 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 80mL min-15vol.%H2/ Ar mixed gas, at 250 DEG C 5h is reacted, and the results are shown in Table 1.
Embodiment 5
By Ni, Cu metal dust (particle size of Ni, Cu metal dust is respectively 200 mesh, 400 mesh) that mass ratio is 1/6
Even mixing is simultaneously filled in the W metal pipe inside composition anode of external diameter 10mm, internal diameter 8mm, length 16cm, then by diameter 10mm,
The negative electrode graphite rod of length 12cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, by reaction cavity
Mixed gas to the pressure that pressure is evacuated to be re-filled with methane that volume ratio is 8/1 and ammonia after 5Pa is 0.08MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 3h in the case where electric current is 50A, will
Product natural subsidence 5h and collection obtain NiCu6@NG catalyst；
Weigh a certain amount of NiCu6@NG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 50mL min-15vol.%H2/ Ar mixed gas, at 250 DEG C 6h is reacted, and the results are shown in Table 1.
Embodiment 6
By Co, Cu metal dust (particle size of Co, Cu metal dust is respectively 300 mesh, 500 mesh) that mass ratio is 3/8
Even mixing is simultaneously filled in the Ni metal pipe inside composition anode of external diameter 10mm, internal diameter 7mm, length 18cm, then by diameter 10mm,
The negative electrode graphite rod of length 18cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, by reaction cavity
It is 0.05MPa that pressure is evacuated to be re-filled with methane gas to pressure after 7Pa, is then close on anode and negative electrode electric to producing
Arc discharge and plasma, and electric current be 20A under react 6h after close power supply, by product natural subsidence 6h and collection be
Obtain Co3Cu8@G catalyst；
Weigh a certain amount of Co3Cu8@G catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 4h at 250 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 10h is reacted, and the results are shown in Table 1.
Embodiment 7
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 1/3
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
Degree 16cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum to pressure is that methane that volume ratio is 4/1 and mixed gas to the pressure of hydrogen sulfide are re-filled with after 10Pa is 0.06MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 4h in the case where electric current is 40A, will
Product natural subsidence 5h and collection obtain FeNi3@SG catalyst；
Weigh a certain amount of FeNi3@SG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 8
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 1/3
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
Degree 16cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum to pressure is that methane that volume ratio is 5/1 and mixed gas to the pressure of hydrogen phosphide are re-filled with after 10Pa is 0.06MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 4h in the case where electric current is 40A, will
Product natural subsidence 5h and collection obtain FeNi3@PG catalyst；
Weigh a certain amount of FeNi3@PG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 9
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 1/3
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
Degree 16cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum to pressure is that methane that volume ratio is 2/1 and mixed gas to the pressure of diborane are re-filled with after 10Pa is 0.06MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 4h in the case where electric current is 40A, will
Product natural subsidence 5h and collection obtain FeNi3@BG catalyst；
Weigh a certain amount of FeNi3@BG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 10
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 1/3
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 8mm, internal diameter 6mm, length 14cm, then by diameter 8mm, length
Degree 16cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum is 0.06MPa to be re-filled with methane gas to pressure after 6Pa to pressure, and then anode and negative electrode are close to generation electric arc
Electric discharge and plasma, and electric current be 30A under react 5h after close power supply, by product natural subsidence 6h and collection obtain final product
To FeNi3@G catalyst；
Weigh a certain amount of FeNi3@G catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 3h at 340 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 100mL min-15vol.%H2/ Ar mixed gas, at 300 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 11
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 1/8
Even mixing is simultaneously filled in the W metal pipe inside composition anode of external diameter 10mm, internal diameter 8mm, length 16cm, then by diameter 8mm,
The negative electrode graphite rod of length 18cm be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, by reaction cavity
Mixed gas to the pressure that pressure is evacuated to be re-filled with methane that volume ratio is 3/1 and ammonia after 10Pa is 0.08MPa, so
Anode and negative electrode are close to generation arc discharge and plasma afterwards, and power supply is closed after reacting 4h in the case where electric current is 40A, will
Product natural subsidence 5h and collection obtain FeNi8@NG catalyst；
Weigh a certain amount of FeNi8@NG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 200 DEG C 8h is reacted, and the results are shown in Table 1.
Embodiment 12
By Fe, Ni metal dust (particle size of Fe, Ni metal dust is respectively 400 mesh, 200 mesh) that mass ratio is 6/1
Even mixing is simultaneously filled in composition anode inside the W metal pipe of external diameter 8mm, internal diameter 6mm, length 16cm, then by diameter 8mm, length
Degree 18cm negative electrode graphite rod be fixed on the copper utensil of water-cooled and with above-mentioned anode material level of relative, reaction cavity is taken out
Vacuum to pressure is that methane that volume ratio is 3/1 and mixed gas to the pressure of ammonia are re-filled with after 10Pa is 0.08MPa, then
Anode and negative electrode are close to generation arc discharge and plasma, and power supply is closed after reacting 3h in the case where electric current is 50A, will be anti-
Answer product natural subsidence 4h and collection obtains Fe6Ni@NG catalyst；
Weigh a certain amount of Fe6Ni@NG catalyst fillings enter in fixed bed reactors.Flow velocity is first passed through for 50mL min-1's
5vol.%H2/ Ar gases carry out pretreatment 2h at 300 DEG C to catalyst, then pass to flow velocity for 50mL min-1CO2With
Flow velocity is 20mL min-15vol.%H2/ Ar mixed gas, at 250 DEG C 6h is reacted, and the results are shown in Table 1.
Table 1 be embodiment 1-12 in catalyst to carbon dioxide conversion for carbon monoxide performancea
aReaction condition：100mg catalyst (note：Except A in catalyst prepared by the present inventionxByThe quality of alloy nano particle contains
The mass content of nonmetalloid (Graphene G or nonmetal doping Graphene MG) is outside amount.But the non-gold
The content of doping nonmetalloid M is less in category element doping Graphene MG, only the 0.1 of nonmetal doping Graphene MG
～1%, quantitative deviation is larger, then elocutionary meaning is little).
Fig. 1 FeNi3The transmission electron microscope photo of@G catalyst, as we know from the figure the catalyst distribution is uniform, 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 FeNi3The crystalline substance of alloying pellet
Lattice are 0.21nm, corresponding to (111) crystal face, the thickness of the Graphene G is 0.4nm；
Fig. 3 FeNi3@NG catalyst continuously runs the performance (reaction condition of 200h:100mg FeNi3@NG,50mL min- 1CO2,20mL min-15vol.%H2/ Ar, 200 DEG C), as we know from the figure the catalyst shows good stability.
Claims (10)
1. a kind of graphene coated alloy nano catalyst, it is characterised in that the catalyst includes AxByAlloy nano particle,
And it is coated on the AxByThe Graphene G or nonmetal doping Graphene MG on alloy nano particle surface, 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）.
2. graphene coated alloy nano catalyst according to claim 1, it is characterised in that A in the catalystxBy
The mass content of alloy nano particle is 60～95%.
3. graphene coated alloy nano catalyst according to claim 1 and 2, it is characterised in that the nonmetallic unit
Nonmetalloid M is at least one in N, S, P, B in plain doped graphene MG, in the nonmetal doping Graphene MG
The mass content of nonmetalloid M is 0.1～1%.
4. the graphene coated alloy nano catalyst according to any one of claim 1-3, it is characterised in that described
AxByThe particle size of alloy nano particle is 4～14 nm.
5. the graphene coated alloy nano catalyst according to any one of claim 1-4, it is characterised in that the stone
The thickness of black alkene G or nonmetal doping Graphene MG is 0.2～2 nm.
6. a kind of preparation method of the graphene coated alloy nano catalyst as any one of claim 1-5, its feature
It is, including：
Be filled in inside metal tube after A metal dusts and B metal dusts are uniformly mixed according to mass ratio, and with the metal tube
Composition anode；
Using graphite rod as negative electrode and the anode level of relative, in the mixed gas containing methane or methane and impurity gas
Reaction cavity under 20～60 A arc discharge react 1～6 hour, obtain graphene coated alloy nano catalysis
Agent.
7. preparation method according to claim 6, it is characterised in that the grain of the A metal dusts or/and B metal dusts
Footpath size is 100～500 mesh.
8. the preparation method according to claim 6 or 7, it is characterised in that before the arc discharge reacts, will react
Cavity is evacuated to 5～20 Pa, then passes to the mixed gas of methane or methane and impurity gas, the methane or methane
It is 0.05～0.09 MPa with the pressure of the mixed gas of impurity gas.
9. the preparation method according to any one of claim 6-8, it is characterised in that the body of the methane and impurity gas
Product is than being 9:1～1:9, the impurity gas is at least one in ammonia, hydrogen sulfide, hydrogen phosphide, diborane.
10. one kind as any one of claim 1-5 graphene coated alloy nano catalyst by carbon dioxide conversion
For the application in carbon monoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611104335.3A CN106622235B (en) | 2016-12-05 | 2016-12-05 | For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611104335.3A CN106622235B (en) | 2016-12-05 | 2016-12-05 | For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106622235A true CN106622235A (en) | 2017-05-10 |
| CN106622235B CN106622235B (en) | 2019-08-16 |
Family
ID=58819127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611104335.3A Active CN106622235B (en) | 2016-12-05 | 2016-12-05 | For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106622235B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046344A (en) * | 2018-07-18 | 2018-12-21 | 辽宁大学 | A kind of preparation method and application of high performance Pd-Zn alloy@C/ZnO composite material |
| CN110575814A (en) * | 2019-08-27 | 2019-12-17 | 中国科学院合肥物质科学研究院 | Graphene-coated metal-based environment functional material and preparation method and application thereof |
| CN110882700A (en) * | 2018-09-11 | 2020-03-17 | 中国石油化工股份有限公司 | Preparation method of gasoline hydrodesulfurization catalyst, gasoline hydrodesulfurization catalyst and application thereof |
| CN111054323A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | InZnOx solid solution structure catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105067586A (en) * | 2015-08-12 | 2015-11-18 | 天津大学 | Nitrogen-doped three-dimensional graphene loaded carbon coated copper substrate material and preparation method |
| CN105268440A (en) * | 2015-11-06 | 2016-01-27 | 河南理工大学 | Graphene loaded cobaltous oxide catalyst and preparation method thereof |
| CN105293492A (en) * | 2015-10-15 | 2016-02-03 | 南开大学 | Method for thermally reducing CO2 to synthesize CO through graphene-based catalyst |
| CN106099104A (en) * | 2016-08-26 | 2016-11-09 | 常开军 | A kind of for secondary cell manufacture without lithium anode material and manufacture method thereof |
-
2016
- 2016-12-05 CN CN201611104335.3A patent/CN106622235B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105067586A (en) * | 2015-08-12 | 2015-11-18 | 天津大学 | Nitrogen-doped three-dimensional graphene loaded carbon coated copper substrate material and preparation method |
| CN105293492A (en) * | 2015-10-15 | 2016-02-03 | 南开大学 | Method for thermally reducing CO2 to synthesize CO through graphene-based catalyst |
| CN105268440A (en) * | 2015-11-06 | 2016-01-27 | 河南理工大学 | Graphene loaded cobaltous oxide catalyst and preparation method thereof |
| CN106099104A (en) * | 2016-08-26 | 2016-11-09 | 常开军 | A kind of for secondary cell manufacture without lithium anode material and manufacture method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOJU CUI ET AL.: "Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation", 《ENERGY ENVIRON. SCI》 * |
| XIN WANG ET AL.: "An electron injection promoted highly efficient electrocatalyst of FeNi3@GR@Fe-NiOOH for oxygen evolution and rechargeable metal–air batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046344A (en) * | 2018-07-18 | 2018-12-21 | 辽宁大学 | A kind of preparation method and application of high performance Pd-Zn alloy@C/ZnO composite material |
| CN110882700A (en) * | 2018-09-11 | 2020-03-17 | 中国石油化工股份有限公司 | Preparation method of gasoline hydrodesulfurization catalyst, gasoline hydrodesulfurization catalyst and application thereof |
| CN110882700B (en) * | 2018-09-11 | 2023-01-13 | 中国石油化工股份有限公司 | Preparation method of gasoline hydrodesulfurization catalyst, gasoline hydrodesulfurization catalyst and application thereof |
| CN110575814A (en) * | 2019-08-27 | 2019-12-17 | 中国科学院合肥物质科学研究院 | Graphene-coated metal-based environment functional material and preparation method and application thereof |
| CN111054323A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | InZnOx solid solution structure catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106622235B (en) | 2019-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wan et al. | Boosting visible-light-driven hydrogen evolution from formic acid over AgPd/2D g-C3N4 nanosheets Mott-Schottky photocatalyst | |
| Xiong et al. | Bismuth-rich bismuth oxyhalides: a new opportunity to trigger high-efficiency photocatalysis | |
| Zhao et al. | Formation of active oxygen species on single-atom Pt catalyst and promoted catalytic oxidation of toluene | |
| Chen et al. | Metal–organic framework-derived porous materials for catalysis | |
| Li et al. | Methane dry reforming over activated carbon supported Ni-catalysts prepared by solid phase synthesis | |
| Xu et al. | Catalytic behavior of carbon supported Ni–B, Co–B and Co–Ni–B in hydrogen generation by hydrolysis of KBH4 | |
| CN109304475A (en) | Carbon-coating nickel composite material and preparation method | |
| CN106622235B (en) | For being the graphene coated alloy nano catalyst and preparation method thereof of carbon monoxide by carbon dioxide conversion | |
| Xu et al. | Thermocatalytic formic acid dehydrogenation: recent advances and emerging trends | |
| Li et al. | Ambient electrosynthesis of ammonia using core–shell structured Au@ C catalyst fabricated by one-step laser ablation technique | |
| US10232355B2 (en) | Carbon nanotube-coated catalyst particle | |
| Liu et al. | Isolated ultrasmall Bi nanosheets for efficient CO2-to-formate electroreduction | |
| Zhang et al. | Octahedral core–shell bimetallic catalysts M@ UIO-67 (M= Pt–Pd nanoparticles, Pt–Pd nanocages): metallic nanocages that enhanced CO2 conversion | |
| Liao et al. | One-step growth of CuO/ZnO/CeO2/ZrO2 nanoflowers catalyst by hydrothermal method on Al2O3 support for methanol steam reforming in a microreactor | |
| Zhang et al. | CoxNi1− x nanoalloys on N-doped carbon nanofibers: Electronic regulation toward efficient electrochemical CO2 reduction | |
| Feng et al. | Copper oxide hollow spheres: synthesis and catalytic application in hydrolytic dehydrogenation of ammonia borane | |
| Yang et al. | Atomically isolated Pd sites within Pd-S nanocrystals enable trifunctional catalysis for direct, electrocatalytic and photocatalytic syntheses of H 2 O 2 | |
| Lee et al. | Phase-controlled synthesis of thermally stable nitrogen-doped carbon supported iron catalysts for highly efficient Fischer-Tropsch synthesis | |
| Wu et al. | Dopamine polymer derived isolated single-atom site metals/N-doped porous carbon for benzene oxidation | |
| Li et al. | Production of hydrogen by ammonia decomposition over supported Co3O4 catalysts | |
| Jiang et al. | Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride | |
| Gu et al. | CO x-free hydrogen production via ammonia decomposition over mesoporous Co/Al 2 O 3 catalysts with highly dispersed Co species synthesized by a facile method | |
| Bu et al. | Magnetic recyclable catalysts with dual protection of hollow Co/N/C framework and surface carbon film for hydrogen production from NaBH4 hydrolysis | |
| Guo et al. | Recent advances in nonmetallic atom-doped metal nanocrystals: Synthesis and catalytic applications | |
| Wang et al. | Electronic transfer enhanced coral-like CoxP loaded Ru nanoclusters as efficient catalyst for hydrogen generation via NaBH4 hydrolysis |
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 |