CN104801341B - A kind of electrochemistry formated catalyst Cu3(BTC)2Method and its NH3SCR is applied - Google Patents
A kind of electrochemistry formated catalyst Cu3(BTC)2Method and its NH3SCR is applied Download PDFInfo
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Abstract
The present invention relates to electrochemistry formated Cu3(BTC)2Method, belong to the preparation technology field of catalysis material and nano material.The methyl imidazolium bromide of 1 butyl 3, trimesic acid, methyl alcohol and alcohol mixed solution are prepared, copper electrode is anode, and platinum electrode is negative electrode, adjusting applied voltage electrolysis with ethylenediamine tetra-acetic acid and diethylenetriamine mixed solution obtains final product Cu3(BTC)2Material.Raw materials of the present invention are cheap and easy to get, and operation is simple, and preparation method is simple, it is easy to control, and equipment requirement is low and environmental protection, Cu3(BTC)2Material be in regular octahedron structure, a diameter of 10 20nm, specific surface area is in 950m2g‑1.The test condition of reaction is：500ppm NO, 500ppmNH3, 5%O2, N2Used as balanced gas, the total flow of flue gas is 100ml/min, and denitration catalyst efficiency reaches 100% at 230 280 DEG C.
Description
Technical field
The present invention relates to electrochemistry formated Cu3(BTC)2Method, belong to catalysis material and nano material preparation technology neck
Domain, is related specifically to the preparation of the metal organic framework compound MOF materials of the small size (100-300nm) of structure-controllable.This
Invention is applied to denitrating flue gas field, is related to Cu3(BTC)2Material removes nitrogen oxygen with selective catalytic reduction for catalyst
Compound.
Background technology
Nitrogen oxides (NOx) is one of main source of atmosphere pollution, mainly includes NO and NO2.With China's economy
Development, vehicle exhaust, the discharge capacity of factory smoke increase year by year, and the environmental hazard caused by nitrogen oxides in flue gas is also gradually
Manifest.Acid rain and photochemical fog it is serious had influence on animals and plants health and ecological environment.
At present, in the removal methods of numerous nitrogen oxides, denitrating flue gas obtain extensive concern both domestic and external, wherein NH3-
SCR method denitration efficiencies are high, the advantages of in the absence of secondary pollution and commonly used.SCR catalyst mainly includes precious metal catalyst
Agent, molecular sieve catalysts and metal oxide and catalyst, wherein V2O5-WO3/TiO2As currently the only for commercial
Catalyst, but it is high to there is reaction temperature in its operation, temperature window it is narrow and, produce N2The vanadium contained in O and catalyst has
Many deficiencies such as toxicity.So seeking grinding for high catalytic activity, many avtive spots and nontoxic catalyst always denitration field
Study carefully focus.
Metal-organic framework materials (MOFs) are mainly by organic ligand and metal ion containing aerobic/nitrogen from group
The novel nano-material with porous network structure skeleton for filling and being formed, heats to MOFs materials under vacuum
Afterwards, it will be removed without influenceing material frame structure in itself with the small solvent molecule of metal-complexing from skeleton, so that
Metal ion in crystal is in unsaturated co-ordination state, occur largely that the metal with outstanding catalytic capability is not in material hole
Saturation site.The features such as having high porosity, structure diversity and big specific surface area just because of it, in catalysis, absorption, passes
Sense, gas storage equal energy source and environmental area extensive application.In numerous MOFs, Cu3(BTC)2(also known as HKUST-1)
It is initially to synthesize and be published on Sciense in researchers such as the Stephen SY.Chui by Hong Kong University of Science and Thchnology in 1999,
Mainly report solvent-thermal process Cu3(BTC)2And the structural property of material.Its Cu2(O2CR)4Construction unit constitutes one
Aperture size is 1 nanometer of three-dimensional open-framework, and, up to 40%, Langmuir specific surface area is up to 917.6m for porosity2g-1.With one
As MOFs materials compare, Cu3(BTC)2With metastable frame structure, stable in the air can exist up to the several months it
Long, and heat endurance also very well, temperature be less than 300 DEG C when structural integrity；The pore passage structure of rule makes it to CO, CO2、CH4、
Some small molecules such as NO are with very strong selective adsorption capacity；Metal active position that is substantial amounts of, being easily obtained becomes one
Plant potential catalyst.The Cu of Amarajothi Dhakshinamoorthy et al. reports3(BTC)2For the contracting of aldehyde and methyl alcohol
Aldehyde reaction, compared with other conventional catalysts (zeolite and clay), transformation efficiency is high, especially Cu3(BTC)2Reaction 8h is to reach
More than 70% conversion ratio.Cu-MOF is applied to CO oxidations by Jing-yun Ye and Chang-jun Liu, is reached at 240 DEG C
100% conversion ratio.But have not yet to see the research report for being applied to remove nitrogen oxides as catalyst.
Prepare Cu3(BTC)2Solvent-thermal method is generally adopted by, the equipment used by the method is simple and crystal mass is high,
Main method through synthesizing as MOFs in recent years.But this kind of synthetic method can only see reaction result, it is impossible to effective observation
There are many uncontrollable factors in course of reaction, and course of reaction influences the property of product., Alberto in 2012
Martinez Joaristi, JanaEt al. reported on Crystal growth＆design with electrification
Method synthesizes several typical MOF materials, such as Cu-MOF, Zn-MOF, Al-MOF etc., and 60 DEG C of Cu-MOF for preparing compare table
Area is up to 1442m2g-1, aperture is 0.6m3g-1.The method reaction time of electrochemistry formated is short, and reaction condition is gently controllable, and
And can effective observing response process.But it still suffers from deficiency in the preparation and structure control of Cu-MOF, it is contemplated that
Optimization electrochemical preparation method, invents a kind of structural behaviour and stablizes controllable, the regular octahedron MOF materials of tactical rule, and makees
It is catalyst NH3- SCR methods remove nitrogen oxides, and catalytic rate is up to 100%.
The content of the invention
The technical problem to be solved in the present invention is prepared with the method for electrochemistry formated with flue gas denitration catalyst activity
Cu3(BTC)2.Specifically using copper platinum electrode respectively as anode and negative electrode, the methylimidazole bromine of electrolyte 1- butyl -3 is added
Compound increases conductance and reaction rate, adds complexing agent regulation voltage and is electrolysed 2.5h, the Cu of anodic oxidation generation2+With it is organic
Ligand reaction obtains required sample.The method raw materials are cheap and easy to get, and operation is simple, and preparation method is simple, it is easy to control,
Equipment requirement is low, and sample yield is high, is a kind of effective preparation method.
Electrochemistry formated Cu3(BTC)2Method, Ni metal2+Obtained by anodic oxidation, in the reaction need not
Slaine is added, can be reacted after connection circuit, the product purity for obtaining is higher.
Technical scheme is as follows：
A kind of electrochemistry formated catalyst Cu3(BTC)2Method, step is as follows：
1) ultrasound pretreatment copper electrode：Prepare 0.1-0.5M KOH, 0.15M K2SO4It is PVA mixed with 0.01-0.05M
Solution A is closed, copper electrode is placed in above-mentioned mixed solution A, the ultrasonically treated 0.5-2h in sonic oscillation pond, then taken out certainly
So dry；
2)Cu3(BTC)2Preparation：The mixing of the methyl alcohol and ethanol of the methyl imidazolium bromide of 1- butyl -3 of 0.03-0.1M
Solution B, to the trimesic acid that 0.06-0.12M is added in above-mentioned mixed solution B, etc. the ethylenediamine tetra-acetic acid (EDTA) of quality
With diethylenetriamine (DEA) common 0.2-0.5M, continue to stir.By step 1) copper electrode that obtains does anode, and platinum electrode does negative electrode,
The 0.5-2.5h of 10.2-14.6V electrolysis at normal temperatures, obtains Cu3(BTC)2Catalyst；
3) dry and activation：By step 2) Cu that obtains3(BTC)2Catalyst ethanol cyclic washing, dries, in N2Protection
Lower 200-280 DEG C of activation 2h, that is, obtain active Cu3(BTC)2Catalyst.
Cu after above-mentioned preparation and activation3(BTC)2Catalyst is used to process the flue gas containing NO, and the test condition of reaction is：
500ppm NO, 500ppm NH3, 5%O2, N2As balanced gas.The total flow of flue gas is 120ml/min, the volume of catalyst
0.04cm-3, therefore air speed 180,000h-1, active testing temperature is 40-300 DEG C.
The present invention proposes electrochemistry formated Cu3(BTC)2Method, using anodic oxidation obtain metal ion, the sample for obtaining
Product crystal formation is homogeneous, and pore passage structure is regular, and specific surface area reaches 950m2g-1, aperture is 0.5m3g-1, the test condition of reaction is：
500ppm NO, 500ppm NH3, 5%O2And N2As balanced gas.The total flow of flue gas is 100ml/min, 230-280 DEG C
Lower denitration catalyst efficiency reaches 100%, is a kind of easy to operate, the flexible environmentally friendly preparation method of method.
Brief description of the drawings
Fig. 1 is the Cu for preparing3(BTC)2XRD.
Fig. 2 (a) is the Cu for preparing3(BTC)2Scanning electron microscope (SEM) photograph.
Fig. 2 (b) is the Cu for preparing3(BTC)2Scanning electron microscope (SEM) photograph.
Fig. 3 is the Cu for preparing3(BTC)2Raman figure.
Fig. 4 is the Cu for preparing3(BTC)2Perspective electron microscope.
Fig. 5 is the Cu for preparing3(BTC)2Thermogravimetric analysis figure.
Fig. 6 is the Cu for preparing3(BTC)2Denitration activity test chart.
Specific embodiment
Describe specific embodiment of the invention in detail below in conjunction with technical scheme.
Embodiment 1
Prepare 0.1M KOH, 0.15M K2SO4With 0.01M polyvinyl alcohol solution, copper electrode is placed in above-mentioned mixing
In solution, the ultrasonically treated 0.5h in sonic oscillation pond then takes out nature and dries；Prepare the first of 1- butyl -3 of 0.03-0.1M
The methyl alcohol of base imidazolium bromide and the mixed solution of ethanol, to the trimesic acid that 0.06-0.12M is added in above-mentioned mixed solution
It is 1 with 0.2-0.5M concentration ratios:1 ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine (DEA), continues to stir.After processing
Copper electrode do anode, platinum electrode does negative electrode, at normal temperatures 10.2-14.6V electrolysis 0.5-2.5h, obtain Cu3(BTC)2Catalysis
Agent, the Cu that will be obtained3(BTC)2Catalyst ethanol cyclic washing, dries, in N2The lower 200-280 DEG C of activation 2h of protection, that is, obtain
Active Cu3(BTC)2Catalyst.
Embodiment 2
Prepare 0.3M KOH, 0.15M K2SO4With 0.03M polyvinyl alcohol solution, the 100W power in sonic oscillation pond
Lower ultrasonic copper electrode treatment 1h, then takes out nature and dries.
Embodiment 3
Prepare 0.5M KOH, 0.15M K2SO4With 0.05M polyvinyl alcohol solution, the 100W power in sonic oscillation pond
Lower ultrasonic copper electrode treatment 2h, then takes out nature and dries.
Embodiment 4
The methyl imidazolium bromide of 1- butyl -3 increases to 0.05M, equal benzene front three during according to reaction in the present invention of embodiment 1
The amount of acid increases to 0.08M, and other raw material dosages and experimental procedure keep constant, and sapphire Cu is obtained3(BTC)2Material.
Embodiment 5
The methyl imidazolium bromide of 1- butyl -3 increases to 0.07M, equal benzene front three during according to reaction in the present invention of embodiment 1
The amount of acid increases to 0.10M, and other raw material dosages and experimental procedure keep constant, and sapphire Cu is obtained3(BTC)2Material.
Embodiment 6
The methyl imidazolium bromide of 1- butyl -3 increases to 0.1M, equal benzene front three during according to reaction in the present invention of embodiment 1
The amount of acid increases to 0.12M, and other raw material dosages and experimental procedure keep constant, and sapphire Cu is obtained3(BTC)2Material.
Embodiment 7
The ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine of equivalent are added during according to reaction in the present invention of embodiment 1
(DEA) common 0.3M, makes applied voltage increase to 11.5V, and other raw material dosages and experimental procedure keep constant, and sky blue is obtained
Cu3(BTC)2Material.
Embodiment 8
The ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine of equivalent are added during according to reaction in the present invention of embodiment 1
(DEA) common 0.4M, makes applied voltage increase to 12.9V, and other raw material dosages and experimental procedure keep constant, and sky blue is obtained
Cu3(BTC)2Material.
Embodiment 9
The ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine of equivalent are added during according to reaction in the present invention of embodiment 1
(DEA) common 0.5M, makes applied voltage increase to 14.6V, and other raw material dosages and experimental procedure keep constant, and sky blue is obtained
Cu3(BTC)2Material.
Embodiment 10
Electrolysis time is reduced to 0.5h during according to reaction in the present invention of embodiment 1, other raw material dosages and experiment step
Suddenly keep constant, sapphire Cu is obtained3(BTC)2Material.
Embodiment 11
Electrolysis time is reduced to 1h during according to reaction in the present invention of embodiment 1, other raw material dosages and experimental procedure
Keep constant, sapphire Cu is obtained3(BTC)2Material.
Embodiment 12
Electrolysis time increases to 2.5h during according to reaction in the present invention of embodiment 1, other raw material dosages and experiment step
Suddenly keep constant, sapphire Cu is obtained3(BTC)2Material.
Embodiment 13
Temperature when being activated according to sample in the present invention of embodiment 1 increases to 220 DEG C, and other conditions keep constant, are obtained
Navy blue Cu3(BTC)2Material.
Embodiment 14
Temperature when being activated according to sample in the present invention of embodiment 1 increases to 250 DEG C, and other conditions keep constant, are obtained
Navy blue Cu3(BTC)2Material.
Embodiment 15
Temperature when being activated according to sample in the present invention of embodiment 1 increases to 280 DEG C, and other conditions keep constant, are obtained
Navy blue Cu3(BTC)2Material.
Claims (1)
1. a kind of electrochemistry formated catalyst Cu3(BTC)2Method, it is characterised in that step is as follows：
1) ultrasound pretreatment copper electrode：Prepare 0.1-0.5M KOH, 0.15M K2SO4It is molten with 0.01-0.05M polyvinyl alcohols
Liquid A, copper electrode is placed in above-mentioned mixed solution A, the ultrasonically treated 0.5-2h in sonic oscillation pond, is then taken out nature and is dried in the air
It is dry；
2)Cu3(BTC)2Preparation：The methyl alcohol and the mixed solution of ethanol of the methyl imidazolium bromide of 1- butyl -3 of 0.03-0.1M
B, to the trimesic acid that 0.06-0.12M is added in above-mentioned mixed solution B, etc. the ethylenediamine tetra-acetic acid and divinyl three of quality
The common 0.2-0.5M of amine, continues to stir；By step 1) copper electrode that obtains does anode, and platinum electrode does negative electrode, at normal temperatures 10.2-
14.6V is electrolysed 0.5-2.5h, obtains Cu3(BTC)2Catalyst；
3) dry and activation：By step 2) Cu that obtains3(BTC)2Catalyst ethanol cyclic washing, dries, in N2Under protection
200-280 DEG C of activation 2h, that is, obtain active Cu3(BTC)2Catalyst.
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| CN106215692B (en) * | 2016-08-03 | 2019-07-30 | 中南大学 | A kind of processing method of carbon based metal organic backbone type oxide catalyst denitrating flue gas |
| CN108130574A (en) * | 2018-01-03 | 2018-06-08 | 苏州大学 | A kind of method of oxygen auxiliary cathode deposited metal organic framework material |
| CN113788462A (en) * | 2021-09-29 | 2021-12-14 | 桂林市农业科学研究中心 | Preparation method for preparing selenium nanoparticles by chemical reduction method |
| CN115304777B (en) * | 2022-04-28 | 2023-06-13 | 北京化工大学 | Electrochemical method for synthesizing columnar copper-based metal-organic framework coating |
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| CN1886536A (en) * | 2003-11-24 | 2006-12-27 | 巴斯福股份公司 | Method for electrochemical production of a crystalline porous metal organic skeleton material |
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| CN103752169A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Metal-organic frame material Cu-BTC for removing nitric oxide with selective catalytic reduction method |
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| US7880026B2 (en) * | 2006-04-14 | 2011-02-01 | The Board Of Trustees Of The University Of Illinois | MOF synthesis method |
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|---|---|---|---|---|
| CN1886536A (en) * | 2003-11-24 | 2006-12-27 | 巴斯福股份公司 | Method for electrochemical production of a crystalline porous metal organic skeleton material |
| CN103451717A (en) * | 2013-09-05 | 2013-12-18 | 太原理工大学 | Preparation method of metal organic polymer material |
| CN103752169A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Metal-organic frame material Cu-BTC for removing nitric oxide with selective catalytic reduction method |
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