CN106345469B - A kind of dendroid Cu/C-CuSiO3 nanostructure hydrogenation catalyst preparation method - Google Patents
A kind of dendroid Cu/C-CuSiO3 nanostructure hydrogenation catalyst preparation method Download PDFInfo
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- CN106345469B CN106345469B CN201610804770.0A CN201610804770A CN106345469B CN 106345469 B CN106345469 B CN 106345469B CN 201610804770 A CN201610804770 A CN 201610804770A CN 106345469 B CN106345469 B CN 106345469B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 241000555268 Dendroides Species 0.000 title claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 9
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 229910001431 copper ion Inorganic materials 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 238000011946 reduction process Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000004907 flux Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002420 X-ray excited Auger electron spectroscopy Methods 0.000 description 1
- NSVHEPGUBVSHMK-UHFFFAOYSA-N [Cu].[Si](O)(O)(O)O Chemical compound [Cu].[Si](O)(O)(O)O NSVHEPGUBVSHMK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J23/72—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of dendroid Cu/C-CuSiO3Nanostructure hydrogenation catalyst and preparation method thereof.This dendroid Cu/C-CuSiO3The preparation process of nanostructure hydrogenation catalyst are as follows: firstly, the surface hydrolysis by ethyl orthosilicate in monodispersed carbon nanotube forms coated with silica layer；Then, coated with silica layer and copper ammonia complexation ionic reaction generate cupric silicate needle array outside carbon nanotube under hydrothermal conditions；Finally, adjusting the content of metallic copper and cupric silicate in material surfaces externally and internally carried metal nano copper particle.The dendroid Cu/C-CuSiO prepared by this method3Nanostructure hydrogenation catalyst can realize Cu in copper-based catalysts (I) and Cu (0) active component stabilization coexists and proportion adjustment, simultaneously because the tubular structure that the needle-shaped array of cupric silicate is formed can get biggish specific surface area and gas flux, can efficiently solve copper-based catalysts in high-temperature hydrogenation reaction process crystal grain migration, sintering and copper activity component valence state it is unstable cause inactivation the problem of, catalytic hydrogenation reaction performance is promoted, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of dendroid Cu/C-CuSiO3Nanostructure hydrogenation catalyst and preparation method thereof, the catalysis
Agent copper metal dispersion degree with higher, stable appearance structure and surface C u (I)/Cu (0) double activated component, can be used for being catalyzed
Hydrogenation reaction.
Background technique
Catalytic hydrogenation is one of most important reaction in organic reaction, is had great importance to industrial production application, and
Copper-based catalysts are with its catalyst that is cheap and easy to get and mainly using as numerous catalytic hydrogenations.Industrially it is applied at present
The carrying method that the copper-based catalysts of hydrogenation reaction mostly use greatly infusion process, coprecipitation etc. traditional is made, simple support type
Catalyst is easy to cause that active component dispersion degree is not high, is present in body phase component and does not obtain maximized benefit during the preparation process
With.Meanwhile the active metal for being carried on carrier surface causes metal nanoparticle easy due to weak carrier-metal interaction
Loss, active component and structural instability, easily occur the migration sintering of metal grain during the reaction, and face reactivity
Low, the problems such as stability is poor, severe reaction conditions.In addition, multivalent state copper activity component stable coexist in surface is that hydrogenation reaction obtains
High activity key, however, the strong reducing property under high-temperature hydrogen atmosphere, copper activity component meeting in hydrogenation reaction on catalyst
The chemical valence state of generation changes, so that catalyst activity and stability are poor, therefore, the hydrogenation reaction of research and development more efficient stable is urged
Agent is to realize the critical issue of such reaction process industrial application.
Silicate material is since its structure feature (ply in the centre, and four oxygen atoms occupy four by oxygen-octahedron, silicon atom
Angle), chemical property is stablized, and fusing point is high, therefore silicate catalyst has metal and carrier strong interaction and good anti-
Answer stability.The silicic acid copper product formed in the preparation of copper Si catalyst has the structure and copper component for stablizing copper catalyst important
Effect, while the stable structure of cupric silicate is difficult to be metallic state by copper reduction under middle cryogenic conditions, therefore the regulation of temperature
Coexisting for catalyst multivalent state copper activity component can be achieved, the relative quantity by changing cupric silicate and supported copper can realize catalyst
The modulation of surface different valence state in proportion.In addition, core sheath structure material is quickly grown in catalysis material field in recent years, due to it
The nano structural material of special appearance, in terms of promoting catalyst stability, " sheath " component plays space confinement effect, so that
Growth of active metal " core " component on scale is defined in a certain range, can be prevented poly- in surface migration under atom high temperature
Collection is grown up and is sintered, the dispersibility and stability of active metal, to promote catalytic perfomance.
In addition, carbon nanomaterial have some unique structures and physicochemical properties, especially higher specific surface area,
Adsorption activation to hydrogen and the excellent properties for promoting its overflow.Therefore, using carbon nanotube as template, cupric silicate nano material shape
At dendroid composite construction catalyst not only contribute to the dispersion of copper activity component, but also can consolidate between dendritic structure
Surely a certain amount of metal copper nano granules are inlayed, for improving copper activity bit quantity, stabilized copper active component, reduce copper nanocrystallite
The migration sintering of grain has remarkable effect.
Summary of the invention
For copper-based catalysts, crystal grain migration, sintering and copper activity component valence state are unstable in high-temperature hydrogenation reaction process
The problem of causing inactivation, the materials such as present invention application conventional oxide, silicate develop low cost, tree easy to operate
Dendritic core sheath structure copper-based catalysts, coupling dendroid unique morphology structure to the facilitation of the active component of catalyst and its
Synergistic effect between component, to achieve the purpose that promote reactivity and stability.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions: being prepared for a kind of dendroid
Cu/C-CuSiO3Nanostructure hydrogenation catalyst.In such nanocatalyst with dendroid core sheath structure, different work in copper
Property component can be restored by control and carry out modulation, the thickness of institute's coated silica layer can pass through the amount for changing silicon source be added
Regulated and controled, the thickness of coated silicic acid layers of copper can be regulated and controled by changing the amount of bivalent cupric ion be added, load
The amount of active ingredient copper can be regulated and controled by changing the load capacity of corresponding precursor.
Dendroid Cu/C-CuSiO provided by the invention3The preparation process of nanostructure hydrogenation catalyst, it is specific to walk
Suddenly it is:
1) CNT@SiO is prepared2Material:
0.1-0.3g cetyl trimethylammonium bromide (CTAB), 30-100mL deionized water, the anhydrous second of 120-400mL
Alcohol, 1-4mL mass fraction 25-28wt% ammonium hydroxide mixing after be stirred at room temperature.A certain amount of carbon is added while being vigorously stirred
Nanotube CNTs (DI=5-100nm) then carries out 0.5~3 hour ultrasonic disperse.0.5- is added dropwise into above-mentioned suspension
3.5mL ethyl orthosilicate continues to be vigorously mixed at room temperature for 4-16 hours.Gained intermediate products are washed.Finally, by from
Son exchange or high-temperature roasting remove structure directing agent.
2) Cu/C-yCuSiO is prepared3Material:
0.01g-1g CNT@SiO2It is scattered in 36-360mL deionized water, ultrasonic disperse is uniform.In the case where stirring at low speed
It is added 0.2-20mL ammonium hydroxide (mass fraction 28%), the nitric acid that 0.12-12mL concentration is 0.01-1M is added dropwise into aforesaid liquid
Copper stirs 5 minutes.Above-mentioned suspension is put into water heating kettle and is heated 4-24 hours at 100-180 DEG C.After natural cooling repeatedly
Centrifuge washing product.Then, dry complete at 40-100 DEG C.
3) xCu/C-yCuSiO is prepared3Material:
By 0.5g Cu/C-yCuSiO3Material ultrasonic disperse is in 125ml solvent.Add a certain amount of work into aforesaid liquid
Property component Cu, is rotated at 40~60 DEG C after mixing evenly.It is carried out under nitrogen or argon after thorough solvent evaporated
Roasting.
Compared with prior art, the beneficial effects of the present invention are:
1, copper-based catalysts crystal grain migration, sintering and copper activity component in high-temperature hydrogenation reaction process are efficiently solved
Valence state is unstable to cause the problem of inactivating；
2, realize in copper-based catalysts different Cu active component ratio can modulation, restore the Cu (I) on rear catalyst surface/
The relative scale of Cu (0) is adjustable；
3, the unique dendroid core sheath structure of catalyst increases specific surface area and duct volume, to can get higher
Gas flux.
Detailed description of the invention
Fig. 1 is the method for the present invention preparation dendroid Cu/C-CuSiO3The TEM of nanostructure hydrogenation catalyst different step
Figure；
Fig. 2 is the method for the present invention preparation dendroid Cu/C-CuSiO3The TEM of nanostructure hydrogenation catalyst schemes；
Fig. 3 is the statistical chart of obtained packet silicon thickness and corresponding TEM figure under different preparation parameters；
Fig. 4 is that table after catalyst reduction prepared by the method for the present invention is levied using the Cu LMM XAES stave of Cu2p spectrum and copper
The different Cu in face (I)/Cu (0) ratio；
Specific embodiment (embodiment)
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
0.16g cetyl trimethylammonium bromide (CTAB), 30mL deionized water, 100mL dehydrated alcohol, 2mL mass point
It is stirred at room temperature uniformly after the ammonium hydroxide mixing of number 25-28wt%.0.1g carbon nanotube CNTs is added while being vigorously stirred
(DI=20-40nm), the ultrasonic disperse of 480min is then carried out.The alcoholic solution of ethyl orthosilicate is added dropwise into above-mentioned suspension
(0.6mL TEOS is dissolved in 20mL dehydrated alcohol), continues to be vigorously mixed at room temperature for 12h.Gained intermediate products are washed 3 times, nitre
The alcoholic solution (8g ammonium nitrate is dissolved in 400mL dehydrated alcohol) of sour ammonium washs 3 times.0.2g CNT@SiO2Be scattered in 40mL go from
In sub- water, ultrasonic disperse is uniform.Lower addition 2mL ammonium hydroxide (mass fraction 25-28%) is being stirred at low speed, is being added dropwise into aforesaid liquid
1.2mL concentration is the copper nitrate of 0.1M, is stirred evenly.Above-mentioned suspension is put into water heating kettle and is heated 12 hours at 140 DEG C.
Multiple centrifuge washing product after natural cooling.It is dry complete at 80 DEG C.By 0.5g Cu/C-yCuSiO3Material ultrasonic disperse in
In 125mL solvent.The copper nitrate for adding 0.2g into above-mentioned solution, is rotated at 60 DEG C after mixing evenly.It is thoroughly evaporated molten
It is roasted under nitrogen or argon again after agent.
Embodiment 2
The present embodiment is that feed change matches on the basis of embodiment 1.
0.16g cetyl trimethylammonium bromide (CTAB), 30mL deionized water, 100mL dehydrated alcohol, 2mL mass point
It is stirred at room temperature uniformly after the ammonium hydroxide mixing of number 25-28wt%.0.1g carbon nanotube CNTs is added while being vigorously stirred
(DI=20-40nm), the ultrasonic disperse of 480min is then carried out.The alcoholic solution of ethyl orthosilicate is added dropwise into above-mentioned suspension
(0.9mL TEOS is dissolved in 20mL dehydrated alcohol) continues to be vigorously mixed at room temperature for 12 hours.Gained intermediate products are washed 3
Secondary, the alcoholic solution (8g ammonium nitrate is dissolved in 400mL dehydrated alcohol) of ammonium nitrate washs 3 times.0.2g CNT@SiO2It is scattered in 40mL
In deionized water, ultrasonic disperse is uniform.Lower addition 3mL ammonium hydroxide (mass fraction 25-28%) is being stirred at low speed, into aforesaid liquid
The copper nitrate that 1.8mL concentration is 0.1M is added dropwise, stirs evenly.Above-mentioned suspension is put into water heating kettle and is heated at 140 DEG C
12h.Multiple centrifuge washing product after natural cooling.It is dry complete at 80 DEG C.By 0.5g Cu/C-yCuSiO3Material ultrasound point
It dissipates in 125mL solvent.The copper nitrate for adding 0.2g into above-mentioned solution, is rotated at 60 DEG C after mixing evenly.Thoroughly steam
It is roasted under nitrogen or argon again after dry solvent.
Embodiment 3
The present embodiment is the active component type and load capacity for changing load on the basis of embodiment 1.
0.16g cetyl trimethylammonium bromide (CTAB), 30mL deionized water, 100mL dehydrated alcohol, 2mL mass point
It is stirred at room temperature uniformly after the ammonium hydroxide mixing of number 25-28wt%.0.1g carbon nanotube CNTs is added while being vigorously stirred
(DI=20-40nm), the ultrasonic disperse of 480min is then carried out.The alcoholic solution of ethyl orthosilicate is added dropwise into above-mentioned suspension
(0.6mL TEOS is dissolved in 20mL dehydrated alcohol), continues to be vigorously mixed at room temperature for 12h.Gained intermediate products are washed 3 times, nitre
The alcoholic solution (8g ammonium nitrate is dissolved in 400mL dehydrated alcohol) of sour ammonium washs 3 times.0.2g CNT@SiO2Be scattered in 40mL go from
In sub- water, ultrasonic disperse is uniform.Lower addition 2mL ammonium hydroxide (mass fraction 25-28%) is being stirred at low speed, is being added dropwise into aforesaid liquid
1.2mL concentration is the copper nitrate of 0.1M, is stirred evenly.Above-mentioned suspension is put into water heating kettle and is heated 12 hours at 140 DEG C.
Multiple centrifuge washing product after natural cooling.It is dry complete at 80 DEG C.By 0.5g Cu/C-yCuSiO3Material ultrasonic disperse in
In 125mL solvent.The copper nitrate for adding 0.6g into above-mentioned solution, is rotated at 60 DEG C after mixing evenly.It is thoroughly evaporated molten
It is roasted under nitrogen or argon again after agent.
Claims (8)
1. a kind of dendroid Cu/C-CuSiO3Nanostructure hydrogenation catalyst, it is characterised in that: inlay metal copper nano granules
In the tubular structure for coating cupric silicate nano whiskers array as template, outer surface using carbon nanotube, structure xCu/C-
yCuSiO3, wherein x is the mass fraction of supported copper component, and y is the coating thickness that carbon nanotube is formed, carbon nanotube, silicon
Sour copper at least one dimension structure is in nanoscale.
2. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that: prepared
Journey includes CNT@SiO2The synthesis of core sheath structure intermediate.
3. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that metallic copper
The relative amount of nano particle and cupric silicate can carry out modulation, and reduction process forms the Cu (I) and Cu (0) active group of different proportion
Point.
4. dendroid Cu/C-CuSiO according to claim 13The preparation method of nanostructure hydrogenation catalyst, feature
Be the following steps are included:
1) CNT@SiO is prepared2Material:
0.1-0.3g cetyl trimethylammonium bromide (CTAB), 30-100mL deionized water, 120-400mL dehydrated alcohol, 1-
It is stirred at room temperature after the ammonium hydroxide mixing of 4mL mass fraction 25-28wt%, 0.1g carbon nanotube is added while being vigorously stirred
Then CNTs carries out the ultrasonic disperse of 40-480min, 0.5-3.5mL ethyl orthosilicate is added dropwise in Xiang Shangshu suspension, continues
It is vigorously stirred at room temperature 4-16 hours, gained intermediate products is washed, finally, being removed with ion exchange or the method for high-temperature roasting
Structure directing agent；
2) Cu/C-yCuSiO is prepared3Material:
0.01g-1gCNT@SiO2It is scattered in 36-360mL deionized water, ultrasonic disperse is uniform, is stirring at low speed lower addition
The copper nitrate that 0.12-12mL concentration is 0.01-1M is added dropwise into aforesaid liquid, stirs 5min for 0.2-20mL ammonium hydroxide, above-mentioned outstanding
Turbid is put into water heating kettle to be heated 4-24 hours at 100-180 DEG C, multiple centrifuge washing product after natural cooling, then,
It is dry complete at 40-100 DEG C；
3) xCu/C-yCuSiO is prepared3Material:
By 0.5gCu/C-yCuSiO3Material ultrasonic disperse adds a certain amount of copper ions into aforesaid liquid in 125ml solvent
Solution is rotated at 40~60 DEG C after mixing evenly, and thorough solvent evaporated is placed under nitrogen or argon gas protection and is roasted
It burns.
5. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that coated
The thickness and content of silicon dioxide layer can be regulated and controled by changing the amount of silicon source be added.
6. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that coated
The thickness of silicic acid layers of copper can be regulated and controled by changing the amount of bivalent cupric ion be added.
7. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that coated
The pattern of cupric silicate can be regulated and controled by changing hydrothermal condition.
8. dendroid Cu/C-CuSiO according to claim 13Nanostructure hydrogenation catalyst, it is characterised in that loaded
The amount of active component Cu can be regulated and controled by changing the load capacity of its precursor copper ions solution.
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| CN107804854B (en) * | 2017-11-27 | 2020-03-17 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing copper silicate nanotube by using low-grade attapulgite clay |
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| CN110898847B (en) * | 2019-08-14 | 2022-05-20 | 新奥科技发展有限公司 | Composite carrier type catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN111185172A (en) * | 2020-02-13 | 2020-05-22 | 石河子大学 | High-activity catalyst for dimethyl oxalate hydrogenation reaction and preparation method thereof |
| CN114192164A (en) * | 2021-12-24 | 2022-03-18 | 山东氢谷新能源技术研究院 | Au @ silicate core-shell nano-structure catalyst and preparation method thereof |
| CN115672323A (en) * | 2022-10-25 | 2023-02-03 | 中国科学院合肥物质科学研究院 | Carbon shell coated metal particle loaded silicon-based catalyst, and preparation method and application thereof |
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