CN103143361A - Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof - Google Patents
Graphene-promoted hydrotalcite-based denitration catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene-promoted hydrotalcite-based denitration catalyst and a preparation method thereof, belonging to the technical field of environmental protection catalysts. The chemical formula of the catalyst is M<2+>2Mg<2+>Al<3+>(O), wherein M<2+> is one or a combination of more of Cu<2+>, Co<2+>, Ni<2+> and Mn<2+>, and the mole ratio of M<2+> to Mg<2+> to Al<3+> is 2: 1: 1; and the catalyst has the specific surface area of 80-110 m<2>/g and the pore volume of 0.3-0.4 cc/g, and the pore size distribution is of mesoporous distribution. According to the catalyst, hydrotalcite (LDHs) nanosheets are loaded to the surface of graphene through a co-precipitation method, and M<2+>2Mg<2+>Al<3+>(O) is obtained after calcinations. The catalyst and the preparation method of the catalyst have the advantages that the catalyst has high catalytic activity and better stability to the storage capacity of NOx, is much better than a graphene-promoted-free hydrotalcite-based catalyst and has enhanced direct NO decomposition capability.
Description
Technical field
The invention belongs to the catalysts for environmental protection technical field, a kind of Graphene promoted type hydrotalcite denitrating catalyst and preparation method thereof particularly is provided.
Technical background
Since entering 21st century, development along with national economy and transportation, directly having driven the motor vehicle industry constantly pushes ahead, make output and the recoverable amount of motor vehicle increase sharply, this is when the life of giving us offers convenience, and the environment of also depending on for existence to us has caused serious pollution.Wherein, NO in motor-vehicle tail-gas
xDischarging (being mainly NO) become one of main source of atmospheric pollution, the photochemical fog and the acid rain that form have thus caused serious threat to urban environment and public health.Consider the efficient utilization to fossil fuel, lean-burn automotive will be the development trend of following motor vehicle, therefore, under lean-burn condition to NO
xRemove and become of field of Environment Protection study hotspot and difficult point.In numerous denitration technologies, nitrogen oxide storage and reduction technology (NO
xStorage-Reduction, NSR) be that moving source removes NO
xThe Development Technology of tool prospect.Storge quality is the very important feature that the NSR catalyst has, and it directly affects NO
xRemoving fully under proper condition, so its NOx storage amount (NO
xStorage Capacity, NSC) be an importance investigating the catalyst activity height.
Hydrotalcite (LDHs) is by positively charged laminate and interlayer anion ordered fabrication and the lamellar compound that forms, and its chemical composition can be expressed as with general formula: [M
2+ 1-xM
3+ x(OH)
2]
x+(A
n-)
x/nMH
2O, wherein M
2+And M
3+Be respectively divalence and trivalent metal cation on the main body laminate, A
n-Be interlayer anion, x (=M
3+/ (M
2++ M
3+)) be molar ratio.The composite metal oxide that obtains as the presoma roasting take LDHs has distributions of metallic elements homogeneous and intrinsic alkalescence concurrently, has direct decomposition, storage and reduction multifunctionality in denitration reaction, thereby be subject to extensive concern in the NSR technical research.Yet, usually larger by the LDHs particle diameter of traditional co-precipitation method preparation, and easy sintering in high-temperature roasting.Therefore the composite metal oxide that is obtained by the roasting of LDHs precursor exists usually that specific area is little, the shortcoming of particle bad dispersibility, thereby makes the catalyst activity decreased.There are some researches show again simultaneously that higher this shortcoming performance of sintering temperature is more obvious.As 2009, Li etc. reported in Applied Catalysis B:Environmental the 91st volume 406-415 page, by the LDHs base Co of coprecipitation preparation
2.5Mg
0.5The AlO O composite metallic oxide catalyst reduces rapidly with the NOx storage amount that sintering temperature improves catalyst, and this is mainly to reduce and due to Active sites quantity reduces due to specific area that sintering of catalyst causes.
At present, by selecting some suitable carriers, improve the decentralization of nanocatalyst particles and then the research of raising catalytic activity and evoked broad interest.For example, have much about the report of New Type of Carbon carrier such as carbon fiber (CF), active carbon (AC) and CNT (CNT) even load metal simple-substance/metal oxide in recent years.2011, the people such as Li reported CNT (CNT) supported V at Journal of Hazardous Materials the 192nd volume 915-921 page
2O
5/ TiO
2Catalyst, the facilitation of CNT show specific area and the pore volume that has improved catalyst, thereby provide more active sites for catalytic reaction.2012, Graphene (Graphene) load Au, Pt, Pd nano-particle catalyst that the people such as Xu report in The Journal of Physical Chemistry C the 112nd volume 19841-19845 page demonstrate huge application potential at catalytic field, and wherein very important reason is exactly that the Graphene carrier is to the peptizaiton of active component.Above example explanation selects suitable carbon carrier can improve the decentralization of metal simple-substance or metal oxide, thereby improves catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of Graphene promoted type hydrotalcite denitrating catalyst and preparation method thereof.Easy and the mild condition of preparation process, without any need for organic reagent, hydrotalcite nano chip size homogeneous and high dispersive in the graphene-supported hydrotalcite composite material of gained.After roasting, resulting Graphene promoted type hydrotalcite catalyst demonstrates excellent NO in denitration reaction
xStorage capacity and decomposability are owing to the high dispersive facilitation of Graphene to active component.
Graphene oxide is metal cation at first initial preparation adsorbs salting liquid with electrostatic force, growth and the reunion of hydrotalcite nucleus have been suppressed in nucleation process, thereby obtain the hydrotalcite catalyst of high dispersive, size homogeneous, and then overcome the not high shortcoming of the general NOx storage amount of hydrotalcite catalyst in prior art.This catalyst under lean-burn condition to NO
xRemove and presented very high storage capacity and direct decomposability preferably, greatly be better than without Graphene promoted type hydrotalcite catalyst, simultaneously easy, the mild condition of preparation process.Catalyst recycling 4 times, storage capacity, resolution ratio remain unchanged substantially, show that catalyst has higher stability.
The chemical formula of Graphene promoted type hydrotalcite denitrating catalyst of the present invention is M
2+ 2Mg
2+Al
3+(O); Wherein, M
2+Be Cu
2+, Co
2+, Ni
2+, Mn
2+In one or more combination, M
2+: Mg
2+: Al
3+Mol ratio be 2:1:1; Specific surface area of catalyst is 80～110 m
2/ g, pore volume are 0.3～0.4 cc/g, and pore-size distribution is mesoporous distribution.
This catalyst is carried on Graphene (Graphene) surface by coprecipitation with hydrotalcite (LDHs) nanometer sheet, obtains M after roasting
2+ 2Mg
2+Al
3+(O).
Graphene of the present invention promotes that the preparation method of hydrotalcite catalyst is at first with a certain proportion of M
2+(Cu
2+, Co
2+, Ni
2+, Mn
2+In one or more combination), Mg
2+, Al
3+Salting liquid mix with graphene oxide colloidal solution, the metal cation Electrostatic Absorption is in graphene oxide surface, then original position generates the hydrotalcite nano piece of small particle diameter, high dispersive under alkaline environment, obtains corresponding catalyst after roasting.Specifically comprise the steps:
(1) pre-oxidation of graphite: successively with dense H
2SO
4, K
2S
2O
4And P
2O
5Join in flask, add graphite powder under stirring, at last 60～80
oReacted in the C water-bath 6～8 hours, washing is to neutral, and is dry, standby; Graphite wherein: dense H
2SO
4: K
2S
2O
4: P
2O
5Mass ratio be 1:4～8:0.5:0.5.
(2) preparation of graphene oxide: measure dense H in four-hole boiling flask
2SO
4, 0～10
oUnder the C stirring condition successively with pre-oxidation graphite powder and NaNO
3Join dense H
2SO
4In, and slowly add KMnO
4, stirring reaction 60～90 minutes; Then flask is transferred to 35
oIn the water bath with thermostatic control of C, continue to stir 30～60 minutes; Add at last deionized water in stirring, control reaction temperature in 95～98
oBetween C, continue to stir 30～60 minutes; Use 3% H
2O
230～50 ml processing reaction liquid are to presenting golden yellow, then filter while hot, more fully wash to the filtrate without SO4 with 5% HCl and deionized water
2-Graphite wherein: dense H
2SO
4: NaNO
3: KMnO
4Mass ratio be 1:42:0.5:3, dense H
2SO
4: H
2The volume ratio of O is 1:2.
(3) M
2+ 2Mg
2+Al
3+(O) preparation of catalyst: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, namely obtained finely dispersed graphene oxide colloidal solution in ultrasonic 0.5～2 hour with 100W～1000W frequency under stirring condition, its mass concentration is 2mg/ml; Take 0.007～0.021 mol M
2+(NO
3)
2XH
2O, M
2+Cu
2+, Co
2+, Ni
2+, Mn
2+In one or more combination, 0.0035～0.0105 mol Mg (NO
3)
26H
2O, 0.0035～0.0105 mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in 500 ml graphene oxide colloidal solution, stirs 30～60 minutes and assisting ultrasonic; Again with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, keeps 30～50 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10 ± 0.5; Last 65
oC crystallization 4 hours, centrifugal, washing, 60～80
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtains catalyst after 4 hours and is expressed as M
2+ 2Mg
2+Al
3+(O).
The present invention compared with prior art has the following advantages and characteristics:
(1) prepared hydrotalcite/Graphene (LDH/Graphene) composite with a kind of simple synthetic route, gained carrier stability is high, be easy to that hydrotalcite nano piece disperses, the size homogeneous.
(2) the prepared hydrotalcite denitrating catalyst of the present invention spinelle particle high degree of dispersion, particle diameter are little, and recycled for multiple times still has very high NO
xStorage capacity (NSC) has good commercial application prospect, and hydrotalcite denitrating catalyst of a kind of high storage capacity and preparation method thereof is provided.
Description of drawings
Fig. 1 is the SEM spectrogram of embodiment 1 precursor.
Fig. 2 is the TEM spectrogram of embodiment 1 precursor.
Fig. 3 is gained CATALYST Co after embodiment 1 precursor roasting
2+ 2Mg
2+Al
3+(O) SEM spectrogram.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:
(1) pre-oxidation of graphite: successively with the 24 dense H of ml
2SO
4, 5 g K
2S
2O
4With 5 g P
2O
5Join in flask, add 10 g graphite powders under stirring, at last 80
oIn the C water-bath, reaction is 6 hours, and washing is to neutral, and is dry, standby.
(2) preparation of graphene oxide: measure the 115 dense H of ml in 500 ml flasks
2SO
4, in ice-water bath under stirring condition successively with 5 g pre-oxidation graphite powders and 2.5 g NaNO
3Join dense H
2SO
4In, and slowly add 15 g KMnO
4, stirring reaction 90 minutes; Then flask is transferred to 35 ± 3
oIn the water bath with thermostatic control of C, continue to stir 30 minutes; Add at last 230 ml deionized waters in stirring, control reaction temperature lower than 98
oC continues to stir 30 minutes; Use 3% H
2O
230ml processing reaction liquid is to presenting golden yellow, then filters while hot, fully washs to the filtrate without SO4 with 5% HCl and deionized water
2-
(3) Co
2+ 2Mg
2+Al
3+(O) preparation of catalyst: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with its dilution 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour with deionized water, its mass concentration is 2mg/ml; Take 0.007 mol Co (NO
3)
26H
2O, 0.0035mol Mg (NO
3)
26H
2O, 0.0035mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2Mg
2+Al
3+(O).
Embodiment 2:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.014 mol Co (NO
3)
26H
2O, 0.007mol Mg (NO
3)
26H
2O, 0.007mol Al (NO
3)
39H
2O is dissolved in the 100ml deionized water and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2Mg
2+Al
3+(O).
Embodiment 3:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.021 mol Co (NO
3)
26H
2O, 0.0105 mol Mg (NO
3)
26H
2O, 0.0105 mol Al (NO
3)
39H
2O is dissolved in the 100ml deionized water and pours in 500 ml graphene oxide solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtained CATALYST Co after 4 hours
2+ 2Mg
2+Al
3+(O).
Embodiment 4:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.007 mol Cu (NO
3)
23H
2O, 0.0035 mol Mg (NO
3)
26H
2O, 0.0035 mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtained Catalysts Cu after 4 hours
2+ 2Mg
2+Al
3+(O).
Embodiment 5:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.007 mol Ni (NO
3)
26H
2O, 0.0035 mol Mg (NO
3)
26H
2O, 0.0035 mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, and keeping time for adding is about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtains catalyst n i after 4 hours
2+ 2Mg
2+Al
3+(O).
Embodiment 6:
The present embodiment except following characteristics with embodiment 1: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, obtained finely dispersed graphene oxide colloidal solution under agitation ultrasonic 1 hour, its mass concentration is 2mg/ml; Take 0.007 mol Mn (NO
3)
2, 0.0035mol Mg (NO
3)
26H
2O, 0.0035 mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in graphene oxide colloidal solution, stirs 30 minutes and is aided with ultrasonic; At last with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, keeps about 40 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10; Last 65
oC crystallization 4 hours, centrifugal, washing, 60
oC oven dry, with product in Muffle furnace 500
oIn the C air atmosphere, roasting obtains catalyst Mn after 4 hours
2+ 2Mg
2+Al
3+(O).
Claims (2)
1. a Graphene promoted type hydrotalcite denitrating catalyst, is characterized in that, the chemical formula of this catalyst is M
2+ 2Mg
2+Al
3+(O); Wherein, M
2+Be Cu
2+, Co
2+, Ni
2+, Mn
2+In one or more combination, M
2+: Mg
2+: Al
3+Mol ratio be 2:1:1; Specific surface area of catalyst is 80～110 m
2/ g, pore volume are 0.3～0.4 cc/g, and pore-size distribution is mesoporous distribution;
This catalyst is carried on the Graphene surface by coprecipitation with hydrotalcite nano piece, obtains after roasting.
2. the preparation method of a Graphene promoted type hydrotalcite denitrating catalyst claimed in claim 1, is characterized in that, comprises the following steps:
(1) pre-oxidation of graphite: successively with dense H
2SO
4, K
2S
2O
4And P
2O
5Join in flask, add graphite powder under stirring, at last 60～80
oReacted in the C water-bath 6～8 hours, washing is to neutral, and is dry, standby; Graphite wherein: dense H
2SO
4: K
2S
2O
4: P
2O
5Mass ratio be 1:4～8:0.5:0.5;
(2) preparation of graphene oxide: measure dense H in four-hole boiling flask
2SO
4, 0～10
oUnder the C stirring condition successively with pre-oxidation graphite powder and NaNO
3Join dense H
2SO
4In, and add KMnO
4, stirring reaction 60～90 minutes; Then flask is transferred to 35
oIn the water bath with thermostatic control of C, continue to stir 30～60 minutes; Add at last deionized water in stirring, control reaction temperature in 95～98
oBetween C, continue to stir 30～60 minutes; Use 3% H
2O
230～50 ml processing reaction liquid are to presenting golden yellow, then filter while hot, more fully wash to the filtrate without SO4 with 5% HCl and deionized water
2-Graphite wherein: dense H
2SO
4: NaNO
3: KMnO
4Mass ratio be 1:42:0.5:3, dense H
2SO
4: H
2The volume ratio of O is 1:2.
(3) M
2+ 2Mg
2+Al
3+(O) preparation of catalyst: 1 g graphite oxide is transferred in the 1L four-hole boiling flask, with deionized water, it is diluted 500 ml, namely obtained finely dispersed graphene oxide colloidal solution in ultrasonic 0.5～2 hour with 100W～1000W frequency under stirring condition, its mass concentration is 2mg/ml; Take 0.007～0.021 mol M
2+(NO
3)
2XH
2O, M
2+Cu
2+, Co
2+, Ni
2+, Mn
2+In one or more combination, 0.0035～0.0105 mol Mg (NO
3)
26H
2O, 0.0035～0.0105 mol Al (NO
3)
39H
2O is dissolved in 100 ml deionized waters and pours in 500 ml graphene oxide colloidal solution, stirs 30～60 minutes and assisting ultrasonic; Again with mol ratio [Na
2CO
3]/[Al (NO
3)
39H
2O]=2, [NaOH]/[Na
2CO
3The mixed alkali liquor of]=3.2 drips in flask, keeps 30～50 minutes, and when alkali lye drips end, pH value of solution is stabilized in 10 ± 0.5; Last 65
oC crystallization 4 hours, centrifugal, washing, 60～80
oThe C oven dry; With product in Muffle furnace 500
oIn the C air atmosphere, roasting obtains catalyst after 4 hours and is expressed as M
2+ 2Mg
2+Al
3+(O).
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| CN103769048A (en) * | 2014-01-22 | 2014-05-07 | 中国科学院合肥物质科学研究院 | Preparation method of three-dimensional porous graphene-loaded nanometer magnesium-aluminum hydrotalcite fluorine removal agent |
| CN103769048B (en) * | 2014-01-22 | 2015-11-25 | 中国科学院合肥物质科学研究院 | A kind of preparation method of three-dimensional porous graphene-supported nano magnalium hydrotalcite defluorinating agent |
| CN103920497A (en) * | 2014-04-02 | 2014-07-16 | 北京化工大学 | Preparation method of graphene-loaded ultrathin metal sheet with atomic-scale thickness |
| CN104056629A (en) * | 2014-06-17 | 2014-09-24 | 中国天辰工程有限公司 | Catalyst used in preparation of low-carbon alcohol by synthesis gas, as well as preparation method and application of catalyst |
| CN104190409B (en) * | 2014-08-19 | 2016-08-17 | 南京师范大学 | The low-temperature SCR sulfur resistant catalyst of graphene-supported titanium-based core shell structure and preparation method |
| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
| CN104857960B (en) * | 2015-04-22 | 2017-10-10 | 北京化工大学 | Graphene is oriented to multilevel hierarchy composite oxide catalysts and preparation method thereof |
| CN104857960A (en) * | 2015-04-22 | 2015-08-26 | 北京化工大学 | Graphene-oriented multi-level structure composite oxide catalyst and preparation method thereof |
| CN105289537A (en) * | 2015-10-30 | 2016-02-03 | 广东电网有限责任公司电力科学研究院 | Middle-temperature carbon dioxide solid absorbent and preparation method thereof |
| CN105776261A (en) * | 2016-01-07 | 2016-07-20 | 北京化工大学 | Method for rapid preparation of multi-level structure hydrotalcite and graphene oxide composite material |
| CN108927170A (en) * | 2018-08-17 | 2018-12-04 | 太原理工大学 | A kind of preparation method and application of the low-temperature denitration of flue gas catalyst based on CoMnAl houghite |
| CN108927170B (en) * | 2018-08-17 | 2021-02-05 | 太原理工大学 | Preparation method and application of low-temperature flue gas denitration catalyst based on CoMnAl hydrotalcite-like compound |
| US20220072161A1 (en) * | 2019-01-31 | 2022-03-10 | Anhui University | Graphene quantum dots-gadolinium ion chelate as magnetic resonance imaging contrast agent and preparation method thereof |
| CN113019376A (en) * | 2021-03-18 | 2021-06-25 | 北京化工大学 | Copper-based composite catalyst for growing graphene modified foam nickel substrate and preparation method thereof |
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