CN104525210A - Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix - Google Patents
Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix Download PDFInfo
- Publication number
- CN104525210A CN104525210A CN201410655513.6A CN201410655513A CN104525210A CN 104525210 A CN104525210 A CN 104525210A CN 201410655513 A CN201410655513 A CN 201410655513A CN 104525210 A CN104525210 A CN 104525210A
- Authority
- CN
- China
- Prior art keywords
- mwcnts
- catalyst
- certain amount
- carrier
- logical
- 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.)
- Pending
Links
Abstract
The invention discloses a method for preparing an MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as a matrix through a chemical vapor deposition (CVD) technology, and an application of the catalyst CO preferential oxidation reactions. The MWCNTs carrier used for CO preferential oxidation is prepared by using iron, cobalt and nickel as a matrix through the CVD technology, and a supported CuxO-CeO2 complex is a catalyst prepared from copper nitrate and cerium nitrate through an immersion technology and used for CO preferential oxidation. The conversion rate and the selectivity of the catalyst in CO preferential oxidation are high, and the temperature window of CO complete conversion is wide.
Description
Technical field
The present invention relates to a kind of Cu
xo-CeO
2catalyst, particularly relate to a kind of with iron, cobalt, nickel for matrix CVD prepare MWCNTs and supported copper cerium oxide for the catalyst of preferential oxidation CO.
Background technology
Hydrogen Energy is the important green energy resource of 21st century energy field, is regarded as the most potential clean energy resource.Proton Exchange Membrane Fuel Cells (PEMFC) is one of desirable reforming unit of Hydrogen Energy, in reformed gas after Water gas shift/WGS, the CO of 0.5-1.0vol% can poison the Pt electrode of fuel cell, therefore the content of CO must be reduced to below 10ppm, and the most effective and the most direct method is CO preferential oxidation (CO-PROX).CNT (CNTs) becomes a kind of catalyst carrier with development potentiality gradually with the stuctures and properties of its uniqueness, and copper cerium series catalyst application has the advantages such as cheap, catalytic performance is good in CO-PROX.
The preparation method of CNT has multiple, such as graphite acr method, laser evaporization method, chemical vapour deposition technique, solid-phase pyrolysis, macromolecule pyrolysis synthetic method etc., and the CNT that different preparation methods obtains has very big difference in stuctures and properties.Wherein, chemical vapour deposition technique is simple and productive rate is higher, is suitable for batch production, is applied to industrial circle.
Noelia etc. are with Fe/Al
2o
3for catalyst CVD simulates thermal depolymerization ethylene making multi-walled carbon nano-tubes, find that the output of sintering temperature MWCNTs 650 DEG C time is the highest; Jayaraman etc. are template by CVD with SBA-15, and supported bi-metallic iron and vanadium are catalyst, have prepared good graphited MWCNTs, for the auxiliary electrode of DSSC; Ni etc. take Mo/Co/MgO as catalyst, CH
4for carbon source, grow CNTs by CVD, carry out the dynamics research of methane pyrolysis carbon nano-tube.
Summary of the invention
The present invention seeks in order to provide with iron, cobalt, nickel for matrix CVD prepare MWCNTs and supported copper cerium oxide for the catalyst of preferential oxidation CO, realize with a small amount of metal for catalyst has prepared MWCNTs by CVD on Fe, Co, Ni, and CuO and CeO of the identical molar fraction of load
2, its cost of material is relatively low, and has good CO conversion ratio and selective.
In order to achieve the above object, technical scheme provided by the present invention is: a kind of MWCNTs loaded Cu for preferential oxidation CO
xo-CeO
2catalyst, the carrier of the described catalyst for preferential oxidation CO is the MWCNTs prepared for matrix CVD with iron, cobalt, nickel.
Further, the Cu of the described MWCNTs load grown on the iron-based of preferential oxidation CO
xo-CeO
2catalyst, Fe base does not almost grow CNT, but defines the structure of multilayer carbon-encapsulated iron nano particle.
Further, the Cu of the described MWCNTs load grown on the cobalt-based of preferential oxidation CO
xo-CeO
2catalyst, Co base has grown MWCNTs, and multi-wall carbon nano-tube tube wall is thicker, and the number of plies reaches 20-25 layer.
Further, the Cu of the MWCNTs load of the described Ni-based upper growth for preferential oxidation CO
xo-CeO
2catalyst, Ni base has grown MWCNTs, and multi-wall carbon nano-tube length of tube is greater than 1.5 μm, and pipe shaft is more straight.
With iron, cobalt, nickel for matrix CVD prepare MWCNTs and supported copper cerium oxide for the preparation method of the catalyst of preferential oxidation CO, it comprises the steps:
1, Cu
xo-CeO
2the preparation of/Fe@CNSs catalyst:
(1) preparation of iron-based presoma: take a certain amount of Fe (NO
3)
39H
2o and Al (NO
3)
39H
2o, is placed in the beaker of 100ml, adds 50ml distilled water, ultrasonic to dissolving completely, for subsequent use; Weigh the there-necked flask that a certain amount of urea is placed in 1000ml, add 450ml distilled water, 80 DEG C of oil bath heating, simultaneously mechanical agitation; In flask, dropwise drip above-mentioned mixed solution, do not stop to be stirred to precipitation completely; Aging 24h, filtering and washing, then 80 DEG C of dry 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Fe/Al
2o
3(molar fraction of Fe is 10%).
(2) growth of carrier Fe@CNSs: get a certain amount of presoma Fe/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as Fe@CNSs.
(3) take Fe@CNSs as the preparation of carrier loaded copper cerium oxide catalyst: the Fe@CNSs getting a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the Fe@CNSs after processing; Get the Fe@CNSs carrier after a certain amount of process, drip distilled water to just wet, recording its water absorption is 5ml.Take Cu (NO
3) 3H
2o and Ce (NO
3) 6H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of Fe@CNSs carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ Fe@CNSs catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
2, Cu
xo-CeO
2the preparation of/MWCNTs-Co catalyst:
(1) preparation of cobalt-based presoma: take a certain amount of Co (NO
3)
26H
2o, in the beaker of 50ml, adds 10ml distilled water, ultrasonic to dissolving completely; Take a certain amount of Al
2o
3add in above-mentioned solution, dipping 24h; 80 DEG C of vacuum drying 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Co/Al
2o
3(molar fraction of Co is 10%).
(2) growth of carrier MWCNTs-Co: take a certain amount of presoma Co/Al
2o
3be laid in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally change logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Co.
(3) take MWCNTs-Co as the preparation of carrier loaded copper cerium oxide catalyst: the MWCNTs-Co taking a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the MWCNTs-Co after processing; Take the MWCNTs-Co carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Co carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Co catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
3, Cu
xo-CeO
2the preparation of/MWCNTs-Ni catalyst:
(1) preparation of Ni-based presoma: take a certain amount of Ni (NO
3)
26H
2o and 400 object aluminium powders are placed in the there-necked flask of 1000ml, add 500ml distilled water, abundant mechanical agitation, drip NaOH solution to PH=10 in flask, do not stop to be stirred to precipitation completely.Filtering and washing to PH=7, then 120 DEG C of dryings, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Ni/Al
2o
3(molar fraction of Ni is 10%).
(2) growth of carrier MWCNTs-Ni: take a certain amount of presoma Ni/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Then logical Ar gas, is warming up to 800 DEG C, more logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Ni.
(3) take MWCNTs-Ni as the preparation of carrier loaded copper cerium oxide catalyst: take a certain amount of MWCNTs-Ni grown in the flask of 50ml, add the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the MWCNTs-Ni after processing; Take the MWCNTs-Ni carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Ni carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Ni catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
Adopt technique scheme, technique effect of the present invention has:
1, cost of material of the present invention is relatively low, and the change can passing through preparation condition (the different growing substrate of MWCNTs) realizes the modulation to catalytic performance.
2, carrier of the present invention and catalyst all have higher specific area, there is dispersed Cu preferably in catalyst
2o, CuO, CuO and Cu
2the existence of O can improve CeO
2in the reducing power of lower temperature.
3, the catalyst that prepared by the present invention has good CO conversion ratio and selective, and the temperature window that CO transforms completely is wider.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the CNSs of Fe matrix CVD growth;
Fig. 2 is the transmission electron microscope photo of the MWCNTs of Co matrix CVD growth;
Fig. 3 is the transmission electron microscope photo of the MWCNTs of Ni matrix CVD growth;
Fig. 4 be with iron, cobalt, nickel for matrix CVD prepare MWCNTs and supported copper cerium oxide for the catalyst activity and selectivity figure of preferential oxidation CO.
Detailed description of the invention
Being below embodiment provided by the present invention, is only further illustrate application of the present invention, instead of limits.
Embodiment 1
With iron be matrix CVD prepare MWCNTs and supported copper cerium oxide for the preparation method of the catalyst of preferential oxidation CO, its step comprises:
(1) preparation of iron-based presoma: take a certain amount of Fe (NO
3)
39H
2o and Al (NO
3)
39H
2o is placed in the beaker of 100ml, adds 50ml distilled water, ultrasonic to dissolving completely, for subsequent use; Weigh the there-necked flask that a certain amount of urea is placed in 1000ml, add 450ml distilled water, 80 DEG C of oil bath heating, simultaneously mechanical agitation; In flask, dropwise drip above-mentioned mixed solution, do not stop to be stirred to precipitation completely; Aging 24h, filtering and washing, then 80 DEG C of dry 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Fe/Al
2o
3(molar fraction of Fe is 10%).
(2) growth of carrier Fe@CNSs: get a certain amount of presoma Fe/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as Fe@CNSs.
(3) take Fe@CNSs as the preparation of carrier loaded copper cerium oxide catalyst: the Fe@CNSs getting a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the Fe@CNSs after processing; Get the Fe@CNSs carrier after a certain amount of process, drip distilled water to just wet, recording its water absorption is 5ml.Take Cu (NO
3) 3H
2o and Ce (NO
3) 6H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of Fe@CNSs carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ Fe@CNSs catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
Embodiment 2
With cobalt be matrix CVD prepare MWCNTs and supported copper cerium oxide for the preparation method of the catalyst of preferential oxidation CO, its step comprises:
(1) preparation of cobalt-based presoma: take a certain amount of Co (NO
3)
26H
2o, in the beaker of 50ml, adds 10ml distilled water, ultrasonic to dissolving completely; Take a certain amount of Al
2o
3add in above-mentioned solution, dipping 24h; 80 DEG C of vacuum drying 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Co/Al
2o
3(molar fraction of Co is 10%).
(2) growth of carrier MWCNTs-Co: take a certain amount of presoma Co/Al
2o
3be laid in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally change logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Co.
(3) take MWCNTs-Co as the preparation of carrier loaded copper cerium oxide catalyst: the MWCNTs-Co taking a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, as 80 DEG C of dry 12h in vacuum drying chamber, obtains the MWCNTs-Co after processing; Take the MWCNTs-Co carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Co carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Co catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
Embodiment 3
Prepare MWCNTs with Ni substrate CVD and supported copper cerium oxide for the preparation method of the catalyst of preferential oxidation CO, its step comprises:
(1) preparation of Ni-based presoma: take a certain amount of Ni (NO
3)
26H
2o and 400 object aluminium powders are placed in the there-necked flask of 1000ml, add 500ml distilled water, abundant mechanical agitation, drip NaOH solution to PH=10 in flask, do not stop to be stirred to precipitation completely.Filtering and washing to PH=7, then 120 DEG C of dryings, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Ni/Al
2o
3(molar fraction of Ni is 10%).
(2) growth of carrier MWCNTs-Ni: take a certain amount of presoma Ni/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Then logical Ar gas, is warming up to 800 DEG C, more logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Ni.
(3) take MWCNTs-Ni as the preparation of carrier loaded copper cerium oxide catalyst: take a certain amount of MWCNTs-Ni grown in the flask of 50ml, add the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the MWCNTs-Ni after processing; Take the MWCNTs-Ni carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Ni carrier adds in beaker, and dipping 24h, 80 DEG C of vacuum drying 12h, be laid in black powder in little porcelain boat after grinding; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Ni catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
The carrier adopting said method obtained and catalyst are used for the performance test of CO preferential oxidation: 0.1g carrier or catalyst are placed in micro fixed-bed reactor quartz ampoule, and reaction gas is 1%O
2, 1%CO, 50%H
2with balance N
2gaseous mixture, air speed is 40,000mlg
cat -1h
-1, gas-chromatography on-line analysis uses 5A molecular sieve column separation of C O, O
2and N
2, TDX-01 separation of C O
2and N
2, carrier gas is high-purity helium, and flow velocity is 30mlmin
-1.
Carrier prepared by said method and catalyst are for CO preferential oxidation catalytic performance test result:
The carrier test result of embodiment 1:
When 115 DEG C, CO conversion ratio 24.7%, selective 100%;
When 135 DEG C, CO conversion ratio 43.1%, selective 88.9%;
When 155 DEG C, CO conversion ratio 63.8%, selective 70.9%.
When 175 DEG C, CO conversion ratio 79.7%, selective 56.7%.
When 195 DEG C, CO conversion ratio 67.6%, selective 43.8%.
When 215 DEG C, CO conversion ratio 46.6%, selective 30.1%.
The catalyst test result of embodiment 1:
When 115 DEG C, CO conversion ratio 100%, selective 72.5%;
When 135 DEG C, CO conversion ratio 100%, selective 61.3%;
When 155 DEG C, CO conversion ratio 97.9%, selective 60.0%.
When 175 DEG C, CO conversion ratio 93.1%, selective 56.9%.
When 195 DEG C, CO conversion ratio 73.3%, selective 44.7%.
When 215 DEG C, CO conversion ratio 61.1%, selective 37.2%.
The carrier test result of embodiment 2:
When 115 DEG C, CO conversion ratio 2.4%, selective 100%;
When 135 DEG C, CO conversion ratio 5.5%, selective 75.9%;
When 155 DEG C, CO conversion ratio 15.7%, selective 36.3%.
When 175 DEG C, CO conversion ratio 39.1%, selective 35.6%.
When 195 DEG C, CO conversion ratio 54.9%, selective 31.8%.
When 215 DEG C, CO conversion ratio 43.4%, selective 25.1%.
The catalyst test result of embodiment 2:
When 115 DEG C, CO conversion ratio 100%, selective 77.1%;
When 135 DEG C, CO conversion ratio 100%, selective 65.8%;
When 155 DEG C, CO conversion ratio 98.8%, selective 64.3%.
When 175 DEG C, CO conversion ratio 80.6%, selective 52.1%.
When 195 DEG C, CO conversion ratio 70.9%, selective 45.9%.
When 215 DEG C, CO conversion ratio 70.8%, selective 45.6%.
The carrier test result of embodiment 3:
When 115 DEG C, CO conversion ratio 8.5%, selective 100%;
When 135 DEG C, CO conversion ratio 15.0%, selective 80.4%;
When 155 DEG C, CO conversion ratio 26.4%, selective 57.9%.
When 175 DEG C, CO conversion ratio 40.5%, selective 40.0%.
When 195 DEG C, CO conversion ratio 38.1%, selective 26.3%.
When 215 DEG C, CO conversion ratio 22.2%, selective 15.2%.
The catalyst test result of embodiment 3:
When 115 DEG C, CO conversion ratio 95.0%, selective 77.5%;
When 135 DEG C, CO conversion ratio 99.3%, selective 63.9%;
When 155 DEG C, CO conversion ratio 96.0%, selective 58.2%.
When 175 DEG C, CO conversion ratio 75.9%, selective 42.0%.
When 195 DEG C, CO conversion ratio 57.3%, selective 34.7%.
When 215 DEG C, CO conversion ratio 38.8%, selective 23.5%.
From above-mentioned test, embodiment 1 obtained /Fe@CNSs carrier and Cu
xo-CeO
2/ Fe CNSs catalyst is preferred forms, and it is better active, and selective relatively better, the window transforming CO is completely wider.
Finally it should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (7)
1. with iron, cobalt, nickel for matrix CVD prepare MWCNTs and supported copper cerium oxide for the preparation method of the catalyst of preferential oxidation CO, it is characterized in that: the carrier of the described catalyst for preferential oxidation CO is the MWCNTs prepared for matrix CVD with iron, cobalt, nickel.
2. the MWCNTs loaded Cu grown on the iron-based of preferential oxidation CO according to claim 1
xo-CeO
2catalyst, is characterized in that: Fe base does not almost grow CNT, but defines the structure of multilayer carbon-encapsulated iron nano particle.
3. the MWCNTs loaded Cu grown on the cobalt-based of preferential oxidation CO according to claim 1
xo-CeO
2catalyst, is characterized in that: Co base has grown MWCNTs, and multi-wall carbon nano-tube tube wall is thicker, and the number of plies reaches 20-25 layer.
4. the MWCNTs loaded Cu of the Ni-based upper growth for preferential oxidation CO according to claim 1
xo-CeO
2catalyst, is characterized in that: Ni base has grown MWCNTs, and multi-wall carbon nano-tube length of tube is greater than 1.5 μm, and pipe shaft is more straight.
5. the catalyst for preferential oxidation CO according to claim 2, is characterized in that the preparation method of catalyst:
(1) preparation of iron-based presoma: take a certain amount of Fe (NO
3)
39H
2o and Al (NO
3)
39H
2o is placed in the beaker of 100ml, adds 50ml distilled water, ultrasonic to dissolving completely, for subsequent use; Weigh the there-necked flask that a certain amount of urea is placed in 1000ml, add 450ml distilled water, 80 DEG C of oil bath heating, simultaneously mechanical agitation; In flask, dropwise drip above-mentioned mixed solution, do not stop to be stirred to precipitation completely; Aging 24h, filtering and washing, then 80 DEG C of dry 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Fe/Al
2o
3(molar fraction of Fe is 10%).
(2) growth of carrier Fe@CNSs: get a certain amount of presoma Fe/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as Fe@CNSs.
(3) take Fe@CNSs as the preparation of carrier loaded copper cerium oxide catalyst: the Fe@CNSs getting a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the Fe@CNSs after processing; Get the Fe@CNSs carrier after a certain amount of process, drip distilled water to just wet, recording its water absorption is 5ml.Take Cu (NO
3) 3H
2o and Ce (NO
3) 6H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of Fe@CNSs carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ Fe@CNSs catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
6. the catalyst for preferential oxidation CO according to claim 3, is characterized in that the preparation method of catalyst:
(1) preparation of cobalt-based presoma: take a certain amount of Co (NO
3)
26H
2o, in the beaker of 50ml, adds 10ml distilled water, ultrasonic to dissolving completely; Take a certain amount of Al
2o
3add in above-mentioned solution, dipping 24h; 80 DEG C of vacuum drying 12h, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Co/Al
2o
3(molar fraction of Co is 10%).
(2) growth of carrier MWCNTs-Co: take a certain amount of presoma Co/Al
2o
3be laid in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Logical Ar gas, is warming up to 800 DEG C again, then logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally change logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Co.
(3) take MWCNTs-Co as the preparation of carrier loaded copper cerium oxide catalyst: the MWCNTs-Co taking a certain amount of preparation is placed in the flask of 50ml, adds the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the MWCNTs-Co after processing; Take the MWCNTs-Co carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Co carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Co catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
7. the catalyst for preferential oxidation CO according to claim 4, is characterized in that the preparation method of catalyst:
(1) preparation of Ni-based presoma: take a certain amount of Ni (NO
3)
26H
2o and 400 object aluminium powders are placed in the there-necked flask of 1000ml, add 500ml distilled water, abundant mechanical agitation, drip NaOH solution to PH=10 in flask, do not stop to be stirred to precipitation completely.Filtering and washing to PH=7, then 120 DEG C of dryings, after grinding in Muffle furnace 500 DEG C of roasting 5h, the presoma of obtained carbon nano-tube, is designated as Ni/Al
2o
3(molar fraction of Ni is 10%).
(2) growth of carrier MWCNTs-Ni: take a certain amount of presoma Ni/Al
2o
3be placed in porcelain boat, put into tube furnace, first logical 10h Ar gas emptying air; Be warming up to 650 DEG C, heating rate is 2 DEG C/min, then logical H
2/ Ar (V
h2=10%) reductase 12 h; Then logical Ar gas, is warming up to 800 DEG C, more logical CH
4/ H
2(V
cH4=20%) carbon-source gas, reaction 160min; Finally logical Ar gas, Temperature fall, obtains black powder, is designated as MWCNTs-Ni.
(3) take MWCNTs-Ni as the preparation of carrier loaded copper cerium oxide catalyst: take a certain amount of MWCNTs-Ni grown in the flask of 50ml, add the dense HNO of 25ml
3(68wt.%) solution, ultrasonic reaction 3h; Filtering and washing, to PH=7, is placed in vacuum drying chamber 80 DEG C of dry 12h, obtains the MWCNTs-Ni after processing; Take the MWCNTs-Ni carrier after a certain amount of above-mentioned process, drip distilled water to just wet, recording its water absorption is 5ml, namely soaks the minimum amount required for carrier.Take a certain amount of Cu (NO
3)
23H
2o and Ce (NO
3)
36H
2o is placed in the beaker of 25ml, measures 5ml distilled water and adds in beaker, ultrasonic dissolution; Taking a certain amount of MWCNTs-Ni carrier adds in beaker, dipping 24h, 80 DEG C of vacuum drying 12h, and after grinding, black powder is laid in little porcelain boat; Put into tube furnace, at N
2atmosphere is warming up to 350 DEG C under enclosing, and heating rate is 2 DEG C/min, and 350 DEG C of roasting 3h, Temperature fall, obtains Cu
xo-CeO
2/ MWCNTs-Ni catalyst (mass fraction of CuO is the mol ratio of 20%, Cu and Ce is 1: 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410655513.6A CN104525210A (en) | 2014-11-04 | 2014-11-04 | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410655513.6A CN104525210A (en) | 2014-11-04 | 2014-11-04 | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104525210A true CN104525210A (en) | 2015-04-22 |
Family
ID=52840943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410655513.6A Pending CN104525210A (en) | 2014-11-04 | 2014-11-04 | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104525210A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108124443A (en) * | 2015-09-25 | 2018-06-05 | Lg化学株式会社 | The preparation method of carbon nano-tube of adjustable carbon nanotubes selectivity and the composite material for including the carbon nanotubes thus prepared |
| CN114289033A (en) * | 2021-12-13 | 2022-04-08 | 湖南大学 | Platinum catalyst loaded on flower-like cerium-iron oxide and application of platinum catalyst in catalyzing preferential oxidation of carbon monoxide in hydrogen-rich gas |
| CN114628749A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Reactor utilizing reformed gas tail gas waste heat and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539731A (en) * | 2003-10-28 | 2004-10-27 | 黄德欢 | Method and equipment for preparing Nano carbon tube with multiple walls |
| CN103021762A (en) * | 2012-12-25 | 2013-04-03 | 青岛盛嘉信息科技有限公司 | Method for processing field emission cathode |
| CN103657666A (en) * | 2013-11-29 | 2014-03-26 | 内蒙古大学 | Preparation method of catalyst using multi-walled carbon nanotube as carrier and for preferential oxidation of CO |
-
2014
- 2014-11-04 CN CN201410655513.6A patent/CN104525210A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539731A (en) * | 2003-10-28 | 2004-10-27 | 黄德欢 | Method and equipment for preparing Nano carbon tube with multiple walls |
| CN103021762A (en) * | 2012-12-25 | 2013-04-03 | 青岛盛嘉信息科技有限公司 | Method for processing field emission cathode |
| CN103657666A (en) * | 2013-11-29 | 2014-03-26 | 内蒙古大学 | Preparation method of catalyst using multi-walled carbon nanotube as carrier and for preferential oxidation of CO |
Non-Patent Citations (1)
| Title |
|---|
| 曾尚红等: "制备方法对CuO-CeO2/Al2O3/FeCrAl整体催化剂结构、粘附稳定性和催化性能的影响", 《催化学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108124443A (en) * | 2015-09-25 | 2018-06-05 | Lg化学株式会社 | The preparation method of carbon nano-tube of adjustable carbon nanotubes selectivity and the composite material for including the carbon nanotubes thus prepared |
| CN108124443B (en) * | 2015-09-25 | 2021-07-27 | Lg化学株式会社 | Method for preparing carbon nanotube capable of adjusting selectivity of carbon nanotube and composite material comprising carbon nanotube prepared thereby |
| CN114628749A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Reactor utilizing reformed gas tail gas waste heat and application |
| CN114628749B (en) * | 2020-12-10 | 2024-03-19 | 中国科学院大连化学物理研究所 | Reactor utilizing waste heat of reformed gas tail gas and application |
| CN114289033A (en) * | 2021-12-13 | 2022-04-08 | 湖南大学 | Platinum catalyst loaded on flower-like cerium-iron oxide and application of platinum catalyst in catalyzing preferential oxidation of carbon monoxide in hydrogen-rich gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fu et al. | 2D transition metal dichalcogenides: design, modulation, and challenges in electrocatalysis | |
| Lu et al. | Engineering graphitic carbon nitride (gC 3 N 4) for catalytic reduction of CO 2 to fuels and chemicals: strategy and mechanism | |
| Ran et al. | Defect engineering of photocatalysts for solar energy conversion | |
| Lu et al. | Carbon-based single-atom catalysts for CO 2 electroreduction: progress and optimization strategies | |
| Miao et al. | Molybdenum carbide‐based electrocatalysts for hydrogen evolution reaction | |
| Zhang et al. | Ti3+ self-doped black TiO2 nanotubes with mesoporous nanosheet architecture as efficient solar-driven hydrogen evolution photocatalysts | |
| Zhu et al. | Efficient hydrogen production by photocatalytic water-splitting using Pt-doped TiO2 hollow spheres under visible light | |
| Modak et al. | Metal–organic polymer-derived interconnected Fe–Ni alloy by carbon nanotubes as an advanced design of urea oxidation catalysts | |
| Cheng et al. | Recent Progress of Sn‐Based Derivative Catalysts for Electrochemical Reduction of CO2 | |
| Sun et al. | Photocatalytic and electrocatalytic CO2 conversion: from fundamental principles to design of catalysts | |
| Ma et al. | Molybdenum‐Based Co‐catalysts in Photocatalytic Hydrogen Production: Categories, Structures, and Roles | |
| Wang et al. | Ammonia from photothermal N2 hydrogenation over Ni/TiO2 catalysts under mild conditions | |
| Saraswat et al. | Kinetic study and modeling of homogeneous thermocatalytic decomposition of methane over a Ni–Cu–Zn/Al2O3 catalyst for the production of hydrogen and bamboo-shaped carbon nanotubes | |
| Zhang et al. | g‐C3N4 Nanosheet Nanoarchitectonics: H2 Generation and CO2 Reduction | |
| CN105289498B (en) | A kind of preparation method of biomass carbon carbon nanomaterial compound | |
| Yuan et al. | Ultrafine platinum nanoparticles modified on cotton derived carbon fibers as a highly efficient catalyst for hydrogen evolution from ammonia borane | |
| CN106000405A (en) | Hierarchical porous supported nickel-based catalyst, preparation method and application | |
| Debnath et al. | Recent Developments in the Design of CdxZn1− xS‐Based Photocatalysts for Sustainable Production of Hydrogen | |
| Feng et al. | Ultrafine VN nanoparticles confined in Co@ N-doped carbon nanotubes for boosted hydrogen evolution reaction | |
| CN108666584A (en) | A kind of Co-N-C/ carbon nano-tube catalysts and its preparation method and application | |
| Lin et al. | A review on catalysts for electrocatalytic and photocatalytic reduction of N 2 to ammonia | |
| CN107500296A (en) | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation | |
| Liu et al. | Catkin-derived mesoporous carbon-supported molybdenum disulfide and nickel hydroxyl oxide hybrid as a bifunctional electrocatalyst for driving overall water splitting | |
| CN110116015B (en) | Photocatalyst for completely decomposing water, preparation method and application thereof, reaction method for completely decomposing water through photocatalysis and catalytic mixed solution | |
| Chava et al. | Band structure alignment transitioning strategy for the fabrication of efficient photocatalysts for solar fuel generation and environmental remediation applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150422 |
|
| WD01 | Invention patent application deemed withdrawn after publication |