CN110433838A - A kind of preparation method of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal - Google Patents

A kind of preparation method of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal Download PDF

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CN110433838A
CN110433838A CN201910596164.8A CN201910596164A CN110433838A CN 110433838 A CN110433838 A CN 110433838A CN 201910596164 A CN201910596164 A CN 201910596164A CN 110433838 A CN110433838 A CN 110433838A
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site catalysts
mesoporous carbon
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丁辉
薛凌霄
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Tianjin University
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Abstract

The invention discloses a kind of preparation methods of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal.The catalyst synthesizes a kind of molding monoblock type N doping mesoporous carbon of macroscopic view using CNTs as skeleton.It is a kind of three-dimensional meso-hole carbon material, macroscopically has many advantages, such as that shape-plastic is good, high mechanical strength, solves problem of pressure drop, transport and the storage problem of Industrial Catalysis field catalyst bed；It is microcosmic upper with biggish specific surface area and Kong Rong, mesopore-macropore structure interconnected, to realize macroscopic view and microcosmic good combination.Using monoblock type N doping mesoporous carbon as carrier loaded transition metal atoms, the aggregation of metallic atom can be reduced, disperse metallic atom in the form of atom level, to construct the strong atom level site catalysts of a kind of controlled shape, size adjustable, mechanical stability, it is applied to room-temperature catalytic oxidation degradation VOCs, degradation effect is fabulous, and removal rate can reach 90% or more.

Description

A kind of monoblock type N doping mesoporous carbon atom level active site of carrying transition metal is urged The preparation method of agent
Technical field
The invention belongs to catalyst technical fields and VOCs pollution control field, and in particular to a kind of carrying transition metal The preparation method of monoblock type N doping mesoporous carbon and its at normal temperature application of efficient catalytic degradation VOCs.
Background technique
VOCs is since discharge amount is big, one of the higher significant contributor for being listed in air pollution of toxicity.Therefore, develop VOCs Treatment process is more more and more urgent.Inertial thinking thinks, the catalysis oxidation of VOCs must be in hot conditions (200~400 DEG C) or outer It just can be carried out under the input of boundary's energy, be based on such thinking, catalytic burning, heat accumulating type catalytic burning, low temperature plasma, purple The energy inputs type VOCs such as outer smooth auxiliary catalysis, which clear up technology, becomes mainstream, but these methods often have energy consumption height, safety Low, the problems such as degradation efficiency is low.And room-temperature catalytic oxidation degradation VOCs is with low energy consumption, highly-safe, investment cost is low, nothing two The advantages such as secondary pollution, become most promising VOCs degradation technique.
Under conditions of in normal temperature and pressure and not by outside energy, the reaction rate of VOCs catalysis oxidation is very slow, because This, which designs suitable high activated catalyst, becomes the key for realizing constant temperature catalyzing.The metallic catalyst of atom dispersion is only due to it Special catalytic performance, maximized atomic efficiency and lower cost attracts wide attention rapidly.Atom level active site It can reduce the activation energy of oxidation reaction, and promote to generate the active oxygen species of high redox potential, thus in normal temperature and pressure Lower quickening VOCs oxidizing reaction rate.Studies have shown that noble metal-based catalysts, such as Pt, Pd, Au by adjust particle size and Form has high atom utilization, is used for the constant temperature catalyzing of VOCs with its metallic alloying and carrier coupling Degradation has good catalytic activity and selectivity.
Metal oxide such as MgO, Al2O3、TiO2、Mn2O3、V2O5、Fe2O3、CeO2、La2O3、Cr2O3Deng abundant due to existing Defect sites and its interaction of strong metal-carrier be widely used as the carrier of noble metal catalyst, Publication No. CN The Chinese patent of 106622225 A discloses a kind of monatomic Au catalyst for catalytic degradation VOCs, and monatomic Au is born It is loaded in TiO2In nanometer sheet, catalytic activity and service life with higher；The China of 106807243 A of Publication No. CN is specially Modified Pt is dispersed in MnO by benefit2On, the monatomic catalyst of Pt has been synthesized, room temperature degradation aircraft cabin VOCs has been used for, has Preferable removal effect.But when preparing atom level site catalysts as carrier using metal oxide, metal list original is in carrier Surface is easily moved, and forms cluster and nano particle since higher surface free energy tends to aggregation.
The nano-carbon material porosity controllable because of its biggish specific surface area, height, special chemical property and electro Matter, lower cost are also used for the carrier of the metallic catalyst of atom dispersion, in 107456969 A of Publication No. CN State's patent discloses a kind of atom dispersed catalyst of simple substance brill load carbon nano-fiber, prepares aniline in catalysis hydrogenation of chloronitrobenzene In reaction, excellent catalytic hydrogenation property is shown；The Chinese patent of 109158111 A of Publication No. CN discloses one kind and receives The carbon-based Supported Manganese of rice bores bimetallic catalyst, can be used for catalytic degradation formaldehyde, has preferable effect.But nano-carbon material is general In powder state, problem of pressure drop, therefore the catalysis of powder type can be generated in traditional fixed bed reactor catalyst bed Agent is only applicable to liquid-phase catalysis reaction in practical applications, and transport and recycling difficulty, pole can be also faced in industrial application The earth limits the application in Industrial Catalysis field.
Summary of the invention
The purpose of the present invention is to overcome the disadvantages of the prior art, provides a kind of monoblock type N doping of carrying transition metal The preparation method of mesoporous carbon atom level site catalysts.The catalyst realizes the good knot of micro-scale and macroscopical direction It closes, solves the problem of pressure drop of Industrial Catalysis field catalyst bed, can be used for the constant temperature catalyzing degradation of industrial VOCs, degradation Rate can reach 90% or more.
To achieve the goals above, the technical solution adopted by the present invention is specific as follows:
A kind of preparation method of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal, packet Include following steps:
(1) chemical vapour deposition technique synthesizes CNTs:
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation；
Second step weighs the γ-Al that 5~10g is filtered out2O3Being immersed in 50~100ml mass fraction is 60%~70% Fe(NO3)3In solution, at 20~30 DEG C keep 12~for 24 hours；Then dry 20~30h in 90~120 DEG C of baking oven, then 2~4h is calcined in 350~450 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor；
Third step, by the Fe2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 20~30 DEG C 180~200mlmin-1H220~40min is kept in air-flow, then 400 are risen to the heating rate of 10~20 DEG C/min~ 650 DEG C, reductase 12~3h；Finally, temperature is risen to 750~950 DEG C with the heating rate of 10~20 DEG C/min, and use C2H6With H2Flow is 50mlmin-1It or is 60mlmin-1Mixed gas replace H2, keep 2~3h to grow CNTs, obtain To CNTs crude product；
The CNTs crude product is placed in 200~300ml aqueous slkali, is heated at reflux at 80~150 DEG C by the 4th step 20~30h, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality；It is subsequently placed in 200 In the acid solution of~300ml, it is heated at reflux 10~20h at 80~150 DEG C, to remove remaining metal impurities, and with distillation Water filtering and washing for several times, until cleaning solution is in neutrality；Finally, the first sediment is placed in 100~200 DEG C of baking ovens, dry 20 ~30h obtains CNTs after purification；
(2) cryochemistry fusion method prepares monoblock type N doping mesoporous carbon:
Purifying CNTs, the 4~5g for taking 1~2g step (1) to obtain analyze pure solid glucose and 6~7g analyzes pure solid lemon Lemon acid is uniformly mixed, and 2~3g ammonium carbonate powder is added, and mixing is placed in 100~150 DEG C of baking oven dry 4~6h, then sets In tube furnace, with 2~3 DEG C of min-1Rate be warming up to 350~450 DEG C, in air calcine 3~4h, finally with 5~6 ℃·min-1Rate be warming up to 700~900 DEG C, in He gas anneal 2~4h, obtain monoblock type N doping mesoporous carbon；
(3) infusion process prepares atom level site catalysts:
The first step weighs the monoblock type N doping mesoporous carbon that 2~5g step (2) obtains and is distributed to 20~50ml distilled water In, the salt or acid solution of transition metal is added, forms the first dispersion liquid after mixing, mixes transition metal in the first dispersion liquid with nitrogen The mass ratio of miscellaneous mesoporous carbon is 1:20~1:200；
The boron hydrogen of 0.1~0.5mol/L is added in second step, first dispersion liquid 30~40min of ultrasound that the first step is obtained Change sodium or 10~30ml of solution of potassium borohydride, and be vigorously stirred, until not generating H2, it is reduced metal ion；Then carbon is used It is 7~8 that acid sodium solution, which adjusts pH value of solution, and magnetic agitation heats 3~5h at 60~120 DEG C, until moisture is all evaporated, at this time In the second sediment of gained in transition metal active atom uniform load to the mesoporous carbon carrier of N doping；
The second sediment distilled water and dehydrated alcohol are washed 3~4 times respectively and remove remaining Na by third step+Or K+, it is subsequently placed in 80~150 DEG C of baking ovens dry 2~6h, finally calcines 3 in 350~650 DEG C of air in muffle furnace ~4h obtains atom level site catalysts；
4th step extracts atom level site catalysts, makes the metallic atom high degree of dispersion on carbon carrier, packet Include following steps:
The atom level site catalysts that third step obtains are dispersed in 20~50ml leaching liquor and form the second dispersion Liquid adjusts the second dispersion liquid pH value with sodium carbonate liquor and the metallic atom of supported on carriers is made to reach maximum leaching content, then It is placed in 10~20h of extraction in 50~150 DEG C of oil bath pans, until leaching liquor is all evaporated, is washed with distilled water and filters third precipitating Object 3~4 times, dry 6~15h, 2~5h is finally calcined at 350~650 DEG C, obtains the expensive of high degree of dispersion at 80~150 DEG C Metallic atom grade site catalysts.
Compared with prior art, the present invention has following significant advantage:
(1) mesoporous by a kind of monoblock type N doping of cryochemistry Melting Synthesis using CNTs as skeleton in the present invention Carbon material, as when the carrier of transition metal atoms grade site catalysts, not only having carbon nanometer material in the present invention The nano-meter characteristic of material, such as high specific area, defect sites abundant, the surface for being easy to functionalization, high porosity, high-termal conductivity, heat Stability, chemical stability etc. also have shape-plastic, the macroscopic propertieies such as size adjustable, mechanical strength is big, bed pressure drop is low, The effective combination for realizing micro-scale and macroscopical direction, to solve powdered gold metal catalyst in practical application in industry Problem of pressure drop, transport storage and recycling problem etc..
(2) nitrogen-atoms is introduced into carbon skeleton in the present invention, nitrogen is introduced into the lewis base property point increased in carbon material Position, surface polarity and electron density, increase the quantity of carbon surface defect sites, so as to improve nano-carbon material surface chemistry Property and characteristic electron.In addition, the higher electronegativity of nitrogen-atoms increases the electron donor property of carbon carrier, make in carbon skeleton with The carbon atom of the adjacent band part positive electricity of nitrogen-atoms can be used as the active site of absorption and activate molecular oxygen, promote O and The formation of the free radicals such as OH, to greatly improve the catalytic activity of catalysis oxidation VOCs under room temperature.
(3) the mesoporous carbon carrier of monoblock type N doping in the present invention also has excellent adsorptivity, therefore reacts in catalysis In the process, the mesoporous carbon carrier can also adsorbed target VOCs molecule, make VOCs in active site pre-concentration, increase catalyst with The time of contact of goal response object molecule, significantly improve its catalytic performance.
(4) use ammonium carbonate can also be according to addition carbon by thermal decomposition of ammonium carbonate pore-forming as pore former in the present invention Its porosity is adjusted in the amount of sour ammonium, and making heretofore described catalyst mainly has mesoporous and macropore to constitute, without depositing In micropore, the diffusion phenomena as caused by micropore are avoided, are unfavorable for reactant and the contact in reactivity site and product Desorption, also result in the generation of by-product, reduce the selectivity of catalyst.
(5) using CNTs as carbon skeleton in the heretofore described mesoporous carbon carrier of monoblock type N doping, in the carbon of synthesis CNTs is mutually wound three-dimensional meso-hole structure abundant in carrier, not only increases the specific surface area of carbon carrier, increases work Property site quantity, due also to stablize anchoring metallic atom, prevent its carrier surface assemble, to be conducive to metallic atom Atom level dispersion.
(6) the nitrogen oxygen codope mesoporous carbon atom level site catalysts of transition metal load provided by the invention have Good shape-plastic can be customized its macroscopic form and size according to industrial application, such as spherical, cone Shape, rectangular etc. are readily transported and store.
(7) the nitrogen oxygen codope mesoporous carbon atom level site catalysts of transition metal load provided by the invention can Excellent stability is kept in a long time, and service life is longer, without often more catalyst changeout, greatly reduces degradation VOCs Cost.
It (8) can be through microwave, high temperature or CS after atom level site catalysts inactivation provided by the invention2Carrying out washing treatment is real Existing circular regeneration, the catalyst after regeneration still can reach VOCs treatment effect before inactivation, not only save economic cost, but also meet Green Sustainable strategy.
(9) atom level site catalysts provided by the invention have for the VOCs in constant temperature catalyzing degradation exhaust gas Degradation efficiency height (degradation rate > 90%), reaction condition mild (being not necessarily to high temperature and pressure, can carry out at normal temperatures and pressures) are administered The advantages that at low cost, highly-safe, and can be by the thorough catalytic degradation of VOCs at CO2And water, it is without secondary pollution.
Detailed description of the invention
Fig. 1 is the preparation of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal of the present invention Process schematic；
Fig. 2 is that monoblock type N doping mesoporous carbon atom level site catalysts aoxidize methanol under room temperature in the present invention Catalytic performance test figure；
Fig. 3 is that monoblock type N doping mesoporous carbon atom level site catalysts aoxidize room temperature Toluene in the present invention Catalytic performance test figure；
Fig. 4 is degradation of the monoblock type N doping mesoporous carbon atom level site catalysts to methanol and toluene in the present invention Rate test chart.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
A kind of system of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal of the invention Preparation Method, comprising the following steps:
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube):
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 5~10g is filtered out2O3Being immersed in 50~100ml mass fraction is 60%~70% Fe(NO3)3In solution, at 20~30 DEG C keep 12~for 24 hours.Then dry 20~30h in 90~120 DEG C of baking oven, then 2~4h is calcined in 350~450 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, first in stream at 20~30 DEG C Amount is 180~200mlmin-1H220~40min is kept in air-flow, is then risen to the heating rate of 10~20 DEG C/min 400~650 DEG C, reductase 12~3h.Finally, temperature is risen to 750~950 DEG C with the heating rate of 10~20 DEG C/min, and use C2H6And H2Flow is 50mlmin-1It or is 60mlmin-1Mixed gas replace H2, keep 2~3h to grow CNTs obtains CNTs crude product.
The CNTs crude product that third step obtains is placed in 200~300ml aqueous slkali, next time in 80~150 DEG C by the 4th step Stream 20~30h of heating, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Then It is placed in the acid solution of 200~300ml, is heated at reflux 10~20h at 80~150 DEG C, to remove remaining metal impurities, and For several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, the first sediment is placed in 100~200 DEG C of baking ovens, Dry 20~30h, obtains CNTs after purification.
The aqueous slkali can be one of KOH solution, NaOH solution, and molar concentration is 1~2molL-1；It is described Acid solution can be one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetum, mass fraction be 20~70%.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC):
Purifying CNTs, the 4~5g for taking 1~2g step (1) to obtain analyze pure solid glucose and 6~7g analyzes pure solid lemon Lemon acid is uniformly mixed, and 2~3g ammonium carbonate powder is added, and mixing is placed in 100~150 DEG C of baking oven dry 4~6h, then sets In tube furnace, with 2~3 DEG C of min-1Rate be warming up to 350~450 DEG C, in air calcine 3~4h, finally with 5~6 ℃·min-1Rate be warming up to 700~900 DEG C, in He anneal 2~4h, obtain monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts:
The first step weighs the monoblock type N doping mesoporous carbon that 2~5g step (2) obtains and is distributed to 20~50ml distilled water In, the salt or acid solution of transition metal is added, forms the first dispersion liquid after mixing, mixes transition metal in the first dispersion liquid with nitrogen The mass ratio of miscellaneous mesoporous carbon is 1:20~1:200.
The salt or acid solution of the transition metal can be H2PtCl6、PdSO4、HAuCl4、AgNO3、RuCl3、Rh (NO3)3、OsCl3、H2IrCl6、FeCl3、Co(NO3)2、Ni(NO3)2、Cu(NO3)2One of Deng.
The boron hydrogen of 0.1~0.5mol/L is added in second step, first dispersion liquid 30~40min of ultrasound that the first step is obtained Change sodium or 10~30ml of solution of potassium borohydride, and be vigorously stirred, until not generating H2, it is reduced metal ion.Then carbon is used It is 7~8 that acid sodium solution, which adjusts pH, and magnetic agitation heats 3~5h at 60~120 DEG C, until moisture is all evaporated, gained at this time In second sediment in transition metal active atom uniform load to the mesoporous carbon carrier of N doping.
The second sediment distilled water and dehydrated alcohol are washed 3~4 times respectively and remove remaining Na by third step+Or K+, be placed in 80~150 DEG C of baking ovens dry 2~6h, finally in muffle furnace in 350~650 DEG C of air calcining 3~ 4h obtains atom level site catalysts.
4th step extracts atom level site catalysts, makes the metallic atom high degree of dispersion on carbon carrier, packet Include following steps:
The atom level site catalysts that third step obtains are dispersed in 20~50ml leaching liquor and form the second dispersion Liquid adjusts the second dispersion liquid pH value with sodium carbonate liquor and the metallic atom of supported on carriers is made to reach maximum leaching content, then It is placed in 10~20h of extraction in 50~150 DEG C of oil bath pans, until leaching liquor is all evaporated, is washed with distilled water and filters third precipitating Object 3~4 times, dry 6~15h, 2~5h is finally calcined at 350~650 DEG C, obtains the expensive of high degree of dispersion at 80~150 DEG C Metallic atom grade site catalysts.
The leaching liquor can be NaCN solution, KCN solution, NaClO3Solution, KClO3Solution, Mg (ClO3)2Solution Or one of thiourea solution etc., the Solute mass fraction of leaching liquor are 1~10wt%, preferably 2wt%.In addition, using cyanogen When compound solution is as leaching liquor, need to adjust the second dispersion liquid pH is 11~12；When using solution of chlorate as leaching liquor, need Adjust the second dispersion liquid pH < 7；When using thiourea solution as leaching liquor, the second dispersion liquid pH > 7 need to be adjusted.
Embodiment 1
The preparation of the monoblock type N doping mesoporous carbon (Pt-MNC) of Pt load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 5g is filtered out2O3Fe (the NO that carrier impregnation is 60% in 50ml mass fraction3)3It is molten In liquid, 12h is kept at 20 DEG C.Then the dry 30h in 90 DEG C of baking oven, then 4h is calcined in 350 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 20 DEG C 180ml·min-1H240min is kept in air-flow, then rises to 400 DEG C with the heating rate of 10 DEG C/min, restores 3h.Finally, Temperature is risen to 750 DEG C with the heating rate of 10 DEG C/min, and uses C2H6And H2Flow is 50mlmin-1Mixed gas Instead of H2, keep 3h to grow CNTs, obtain CNTs crude product.
4th step, it is 1molL that the CNTs crude product that third step obtains, which is placed in 200ml concentration,-1KOH solution in, in It is heated at reflux 30h at 80 DEG C, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality. It is subsequently placed in the HCl solution that 200ml mass fraction is 20%, is heated at reflux 20h at 80 DEG C, it is miscellaneous to remove remaining metal Matter, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, put the precipitate in 100 DEG C of baking ovens, it is dry 30h obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 4g for taking 1g step (1) to obtain analyze pure solid glucose and 6g analyzes pure solid citric acid mixing Uniformly, 2g ammonium carbonate powder is added, mixing is placed in 100 DEG C of baking oven dry 6h, is subsequently placed in tube furnace, with 2 DEG C min-1Rate be warming up to 350 DEG C, 4h is calcined in air, finally with 5 DEG C of min-1Rate be warming up to 700 DEG C, in He Anneal 4h, obtains monoblock type N doping mesoporous carbon (MNC).
(3) infusion process prepares Pt-MNC atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 2g step (2) obtains and is distributed in 20ml distilled water, is added H2PtCl6Solution forms the first dispersion liquid after mixing, make the mass ratio 1 of Pt and N doping mesoporous carbon in the first dispersion liquid: 200。
Second step, the first dispersion liquid ultrasound 30min that the first step is obtained, is added the sodium borohydride solution of 0.1mol/L 10ml, and be vigorously stirred, until not generating H2, make Pt4+It is reduced.Then adjusting pH with sodium carbonate liquor is 7, the magnetic at 60 DEG C Power agitating and heating 5h, until moisture is all evaporated, Pt atom uniform load is carried to N doping mesoporous carbon in gained sediment at this time On body.
Second step gained sediment distilled water and dehydrated alcohol are washed 3 times respectively and remove remaining Na by third step+, It is placed in 80 DEG C of baking ovens dry 6h, finally calcines 4h in 350 DEG C of air in muffle furnace, obtains Pt-MNC atom level activity Site catalyst.
4th step extracts Pt-MNC atom level site catalysts, makes the Pt atom high point on carbon carrier It dissipates, comprising the following steps:
It is 1wt% that the Pt-MNC atom level site catalysts that third step obtains, which are dispersed in 20ml Solute mass fraction, NaCN solution in form the second dispersion liquid, with sodium carbonate liquor adjust the second dispersion liquid pH value be 11 so that supported on carriers Pt metallic atom reach maximum leaching content, be subsequently placed in 50 DEG C of oil bath pans and extract 20h, until leaching liquor is all evaporated, use It distills water washing to filter sediment 3 times, dry 15h, finally calcines 5h at 350 DEG C at 80 DEG C, obtains Pt atom high point Scattered atom level site catalysts.
Progress ozone oxygen in fixed-bed reactor is placed in the Pt-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 1 for the catalytic performance test of Pt-MNC atom level site catalysts.
1 Pt-MNC atom level site catalysts catalytic performance test result of table
Embodiment 2
The preparation of the monoblock type N doping mesoporous carbon (Pd-MNC) of Pd load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 10g is filtered out2O3It is immersed in the Fe (NO that 100ml mass fraction is 70%3)3Solution In, it is kept for 24 hours at 30 DEG C.Then the dry 20h in 120 DEG C of baking oven, then 2h is calcined in 450 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 30 DEG C 200ml·min-1H220min is kept in air-flow, then rises to 650 DEG C with the heating rate of 20 DEG C/min, reductase 12 h.Finally, Temperature is risen to 950 DEG C with the heating rate of 20 DEG C/min, and uses C2H6And H2Flow is 60mlmin-1Mixed gas Instead of H2, keep 2h to grow CNTs, obtain CNTs crude product.
4th step, it is 2molL that the CNTs crude product that third step obtains, which is placed in 300ml concentration,-1NaOH solution in, in It is heated at reflux 20h at 150 DEG C, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality. It is subsequently placed in the HNO that 300ml mass fraction is 70%3In solution, it is heated at reflux 10h at 150 DEG C, to remove remaining metal Impurity, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, putting the precipitate in 200 DEG C of baking ovens, do Dry 20h obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 5g for taking 2g step (1) to obtain analyze pure solid glucose and 7g analyzes pure solid citric acid mixing Uniformly, 3g ammonium carbonate powder is added, mixing is placed in 150 DEG C of baking oven dry 6h, is subsequently placed in tube furnace, with 3 DEG C min-1Rate be warming up to 450 DEG C, 3h is calcined in air, finally with 6 DEG C of min-1Rate be warming up to 900 DEG C, in He Anneal 2h, obtains monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 5g step (2) obtains and is distributed in 50ml distilled water, is added PdSO4Solution forms the first dispersion liquid after mixing, make the mass ratio 1:20 of Pd and N doping mesoporous carbon in the first dispersion liquid.
Second step, the first dispersion liquid ultrasound 40min that the first step is obtained, is added the solution of potassium borohydride of 0.5mol/L 30ml, and be vigorously stirred, until not generating H2, make Pd2+Ion is reduced.Then adjusting pH with sodium carbonate liquor is 8, in 120 Magnetic agitation heats 3h at DEG C, until moisture is all evaporated, Pd atom uniform load is situated between to N doping in gained sediment at this time On the carbon carrier of hole.
Second step gained sediment distilled water and dehydrated alcohol are washed 4 times respectively and remove remaining Na by third step+With K+, it is placed in 150 DEG C of baking ovens dry 2h, finally 3h is calcined in 650 DEG C of air in muffle furnace, obtains Pd-MNC atom level Site catalysts.
4th step extracts Pd-MNC atom level site catalysts, makes the Pd atom high point on carbon carrier It dissipates, comprising the following steps:
The atom level site catalysts that third step obtains are dispersed in the KCN that 50ml Solute mass fraction is 10wt% The second dispersion liquid is formed in solution, adjusting the second dispersion liquid pH value with sodium carbonate liquor is 12, so that the Pd of supported on carriers is former Son reaches maximum leaching content, is subsequently placed in 150 DEG C of oil bath pans and extracts 10h, until leaching liquor is all evaporated, is washed with distilled water It filters sediment 4 times, dry 6h, finally calcines 2h at 650 DEG C, obtain the Pd-MNC atom level of high degree of dispersion at 150 DEG C Site catalysts.
Progress ozone oxygen in fixed-bed reactor is placed in the Pd-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 2 for the catalytic performance test of Pd-MNC atom level site catalysts.
2 Pd-MNC atom level site catalysts catalytic performance test result of table
Embodiment 3
The preparation of the monoblock type N doping mesoporous carbon (Au-MNC) of Au load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 7g is filtered out2O3It is immersed in the Fe (NO that 80ml mass fraction is 65%3)3In solution, 20h is kept at 25 DEG C.Then the dry 25h in 100 DEG C of baking oven, then 3h is calcined in 400 DEG C of air, by Fe (NO3)3 It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 25 DEG C 190ml·min-1H230min is kept in air-flow, then rises to 550 DEG C with the heating rate of 15 DEG C/min, reductase 12 .5h.Most Afterwards, temperature is risen to 850 DEG C with the heating rate of 15 DEG C/min, and uses C2H6And H2Flow is 60mlmin-1Mixing Gas replaces H2, keep 2.5h to grow CNTs, obtain CNTs crude product.
4th step, it is 1.5molL that the CNTs crude product that third step obtains, which is placed in 250ml concentration,-1KOH solution in, It is heated at reflux 25h at 100 DEG C, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, in cleaning solution is in Property.It is subsequently placed in the sulfuric acid solution that 250ml mass fraction is 50%, is heated at reflux 15h at 100 DEG C, it is remaining to remove Metal impurities, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, putting the precipitate in 150 DEG C of baking ovens In, dry 25h obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 4.5g for taking 1.5g step (1) to obtain analyze pure solid glucose and 6.5g analyzes pure lemon acid-mixed It closes uniformly, 2.5g ammonium carbonate powder is added, mixing is placed in 120 DEG C of baking oven dry 5h, is subsequently placed in tube furnace, with 2.5℃·min-1Rate be warming up to 400 DEG C, 3.5h is calcined in air, finally with 5.5 DEG C of min-1Rate be warming up to 800 DEG C, anneal 3h in He, obtains monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 3g step (2) obtains and is distributed in 40ml distilled water, is added HAuCl4Solution forms the first dispersion liquid after mixing, make the mass ratio 1 of Au and N doping mesoporous carbon in the first dispersion liquid: 100。
Second step, the first dispersion liquid ultrasound 35min that the first step is obtained, is added the sodium borohydride solution of 0.3mol/L 20ml, and be vigorously stirred, until not generating H2, make Au3+Ion is reduced.Then adjusting pH with sodium carbonate liquor is 7.5, in Magnetic agitation heats 4h at 100 DEG C, until moisture is all evaporated, at this time in gained sediment Au atom uniform load to N doping On mesoporous carbon carrier.
Second step gained sediment distilled water and dehydrated alcohol are washed 3 times respectively and remove remaining Na by third step+, It is placed in 100 DEG C of baking ovens dry 4h, finally 3.5h is calcined in 500 DEG C of air in muffle furnace, obtains Au-MNC atom level Site catalysts.
4th step extracts Au-MNC atom level site catalysts, makes the Au atom high point on carbon carrier It dissipates, comprising the following steps:
It is 2wt%'s that the atom level site catalysts that third step obtains, which are dispersed in 30ml Solute mass fraction, NaClO3The second dispersion liquid is formed in solution, the second dispersion liquid pH < 7 is adjusted with sodium carbonate liquor, so that the Au of supported on carriers Atom reaches maximum leaching content, is subsequently placed in 100 DEG C of oil bath pans and extracts 15h, until leaching liquor is all evaporated, is washed with distillation Wash suction filtration sediment 3 times, dry 10h, finally calcines 3h at 500 DEG C, obtain the Au-MNC atom of high degree of dispersion at 100 DEG C Grade site catalysts.
Progress ozone oxygen in fixed-bed reactor is placed in the Au-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 3 for the catalytic performance test of Au-MNC atom level site catalysts.
3 Au-MNC atom level site catalysts catalytic performance test result of table
Embodiment 4
The preparation of the monoblock type N doping mesoporous carbon (Fe-MNC) of Fe load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 8g is filtered out2O3It is immersed in the Fe (NO that 90ml mass fraction is 70%3)3In solution, It is kept overnight at 23 DEG C.Then the dry 28h in 95 DEG C of baking oven, then 3.5h is calcined in 380 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 23 DEG C 195ml·min-1H235min is kept in air-flow, then rises to 600 DEG C with the heating rate of 20 DEG C/min, restores 3h.Finally, Temperature is risen to 800 DEG C with the heating rate of 15 DEG C/min, and uses C2H6And H2Flow is 60mlmin-1Mixed gas Instead of H2, keep 2.5h to grow CNTs, obtain CNTs crude product.
4th step, it is 1.2molL that the CNTs crude product that third step obtains, which is placed in 300ml concentration,-1KOH solution in, It is heated at reflux 28h at 90 DEG C, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, in cleaning solution is in Property.It is subsequently placed in the acetum that 230ml mass fraction is 40%, is heated at reflux 18h at 100 DEG C, it is remaining to remove Metal impurities, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, putting the precipitate in 120 DEG C of baking ovens In, dry 22h obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 4.2g for taking 1.3g step (1) to obtain analyze pure solid glucose and 6g analyzes pure solid citric acid It being uniformly mixed, 2.2g ammonium carbonate powder is added, mixing is placed in 130 DEG C of baking oven dry 4h, is subsequently placed in tube furnace, with 2.5℃·min-1Rate be warming up to 420 DEG C, 3.5h is calcined in air, finally with 5.5 DEG C of min-1Rate be warming up to 800 DEG C, anneal 3.5h in He, obtains monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 4g step (2) obtains and is distributed in 50ml distilled water, is added FeCl3Solution forms the first dispersion liquid after mixing, make the mass ratio 1:50 of Fe and N doping mesoporous carbon in the first dispersion liquid.
Second step, the first dispersion liquid ultrasound 40min that the first step is obtained, is added the sodium borohydride solution of 0.3mol/L 25ml, and be vigorously stirred, until not generating H2, make Fe3+Ion is reduced.Then adjusting pH with sodium carbonate liquor is 8, in 70 DEG C Lower magnetic agitation heats 5h, until moisture is all evaporated, Fe atom uniform load is mesoporous to N doping in gained sediment at this time On carbon carrier.
Second step gained sediment distilled water and dehydrated alcohol are washed 4 times respectively and remove remaining Na by third step+, It is placed in 90 DEG C of baking ovens dry 5h, finally calcines 3.5h in 600 DEG C of air in muffle furnace, it is living to obtain Fe-MNC atom level Property site catalyst.
4th step extracts Fe-MNC atom level site catalysts, makes the Fe atom high point on carbon carrier It dissipates, comprising the following steps:
The atom level site catalysts that third step obtains are dispersed in the Mg that 25ml Solute mass fraction is 8wt% (ClO3)2The second dispersion liquid is formed in solution, the second dispersion liquid pH < 7 is adjusted with sodium carbonate liquor, so that the Fe of supported on carriers Atom reaches maximum leaching content, is subsequently placed in 80 DEG C of oil bath pans and extracts 18h, until leaching liquor is all evaporated, is washed with distillation Wash suction filtration sediment 3 times, dry 10h, finally calcines 4.5h at 400 DEG C at 140 DEG C, and the Fe-MNC for obtaining high degree of dispersion is former Sub- grade site catalysts.
Progress ozone oxygen in fixed-bed reactor is placed in the Fe-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 4 for the catalytic performance test of Fe-MNC atom level site catalysts.
4 Fe-MNC atom level site catalysts catalytic performance test result of table
Embodiment 5
The preparation of the monoblock type N doping mesoporous carbon (Co-MNC) of Co load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 6g is filtered out2O3It is immersed in the Fe (NO that 60ml mass fraction is 60%3)3In solution, It is kept overnight at 28 DEG C.Then the dry 25h in 105 DEG C of baking oven, then 3h is calcined in 400 DEG C of air, by Fe (NO3)3 It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 28 DEG C 200ml·min-1H225min is kept in air-flow, then rises to 450 DEG C with the heating rate of 10 DEG C/min, restores 3h.Finally, Temperature is risen to 900 DEG C with the heating rate of 10 DEG C/min, and uses C2H6And H2Flow is 50mlmin-1Mixed gas Instead of H2, keep 3h to grow CNTs, obtain CNTs crude product.
4th step, it is 1.8molL that the CNTs crude product that third step obtains, which is placed in 270ml concentration,-1NaOH solution in, It is heated at reflux 23h at 130 DEG C, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, in cleaning solution is in Property.It is subsequently placed in the phosphoric acid solution that 200ml mass fraction is 60%, 14h is heated at reflux at 95 DEG C, to remove remaining gold Belong to impurity, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, put the precipitate in 190 DEG C of baking ovens, Dry 23h, obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 4.4g for taking 1.6g step (1) to obtain analyze pure solid glucose and 6.7g analyzes pure solid citric Acid is uniformly mixed, and 2.7g ammonium carbonate powder is added, and mixing is placed in 120 DEG C of baking oven dry 5.5h, is subsequently placed in tube furnace In, with 3 DEG C of min-1Rate be warming up to 450 DEG C, 3h is calcined in air, finally with 6 DEG C of min-1Rate be warming up to 850 DEG C, anneal 2.5h in He, obtains monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 2.5g step (2) obtains and is distributed in 35ml distilled water, is added Co(NO3)2Solution forms the first dispersion liquid after mixing, make the mass ratio 1 of Co and N doping mesoporous carbon in the first dispersion liquid: 150。
Second step, the first dispersion liquid ultrasound 30min that the first step is obtained, is added the solution of potassium borohydride of 0.2mol/L 15ml, and be vigorously stirred, until not generating H2, make Co2+Ion is reduced.Then adjusting pH with sodium carbonate liquor is 8, in 75 DEG C Lower magnetic agitation heats 4.5h, until moisture is all evaporated, Co atom uniform load is situated between to N doping in gained sediment at this time On the carbon carrier of hole.
Third step washs second step gained sediment distilled water and dehydrated alcohol 3 times respectively, is placed in 130 DEG C of baking ovens Middle dry 4.5h, finally calcines 3h in 650 DEG C of air in muffle furnace, obtains the catalysis of Co-MNC atom level active site Agent.
4th step extracts Co-MNC atom level site catalysts, makes the Co atom high point on carbon carrier It dissipates, comprising the following steps:
The atom level site catalysts that third step obtains are dispersed in the thiocarbamide that 45ml Solute mass fraction is 4wt% The second dispersion liquid is formed in solution, the second dispersion liquid pH > 7 is adjusted with sodium carbonate liquor, so that the Co atom of supported on carriers reaches It to maximum leaching content, is subsequently placed in 130 DEG C of oil bath pans and extracts 19h, until leaching liquor is all evaporated, be washed with distilled water suction filtration Sediment 4 times, dry 15h, finally calcines 4h at 620 DEG C at 120 DEG C, obtains the Co-MNC atom level activity of high degree of dispersion Site catalyst.
Progress ozone oxygen in fixed-bed reactor is placed in the Co-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 5 for the catalytic performance test of Co-MNC atom level site catalysts.
5 Co-MNC atom level site catalysts catalytic performance test result of table
Embodiment 6
The preparation of the monoblock type N doping mesoporous carbon (Ni-MNC) of Ni load
(1) chemical vapour deposition technique synthesis CNTs (carbon nanotube)
The first step, by γ-Al2O3It pulverizes and sieves, retains the part that diameter is 80~150 μm and be used for CNTs growth catalyst Preparation.
Second step weighs the γ-Al that 9g is filtered out2O3Fe (the NO that carrier impregnation is 60% in 100ml mass fraction3)3It is molten In liquid, kept overnight at 30 DEG C.Then drying for 24 hours, then in 420 DEG C of air calcines 2.5h in 110 DEG C of baking oven, will Fe(NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor.
Third step, the Fe that second step is obtained2O3/γ-Al2O3Precursor is placed in tube furnace, is first in flow at 30 DEG C 185ml·min-1H240min is kept in air-flow, then rises to 500 DEG C with the heating rate of 10 DEG C/min, reductase 12 h.Finally, Temperature is risen to 900 DEG C with the heating rate of 20 DEG C/min, and uses C2H6And H2Flow is 60mlmin-1Mixed gas Instead of H2, keep 3h to grow CNTs, obtain CNTs crude product.
4th step, it is 1.8molL that the CNTs crude product that third step obtains, which is placed in 280ml concentration,-1NaOH solution in, It is heated at reflux at 120 DEG C for 24 hours, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, in cleaning solution is in Property.It is subsequently placed in the hydrochloric acid solution that 280ml mass fraction is 30%, is heated at reflux 12h at 120 DEG C, it is remaining to remove Metal impurities, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality.Finally, putting the precipitate in 180 DEG C of baking ovens In, drying for 24 hours, obtains CNTs after purification.
(2) cryochemistry fusion method preparation monoblock type N doping mesoporous carbon (MNC)
Purifying CNTs, the 4.7g for taking 1.8g step (1) to obtain analyze pure solid glucose and 6.8g analyzes pure solid citric Acid is uniformly mixed, and 2.6g ammonium carbonate powder is added, and mixing is placed in 110 DEG C of baking oven dry 5.5h, is subsequently placed in tube furnace In, with 2 DEG C of min-1Rate be warming up to 380 DEG C, 4h is calcined in air, finally with 5 DEG C of min-1Rate be warming up to 750 DEG C, anneal 4h in He, obtains monoblock type N doping mesoporous carbon.
(3) infusion process prepares atom level site catalysts
The first step weighs the monoblock type N doping mesoporous carbon that 3.5g step (2) obtains and is distributed in 30ml distilled water, is added Ni(NO3)2Solution forms the first dispersion liquid after mixing, make the mass ratio 1 of Ni and N doping mesoporous carbon in the first dispersion liquid: 100。
Second step, the first dispersion liquid ultrasound 30min that the first step is obtained, is added the solution of potassium borohydride of 0.4mol/L 15ml, and be vigorously stirred, until not generating H2, make Ni2+Ion is reduced.Then adjusting pH with sodium carbonate liquor is 7, in 80 DEG C Lower magnetic agitation heats 5h, until moisture is all evaporated, Ag atom uniform load is mesoporous to N doping in gained sediment at this time On carbon carrier.
Third step washs second step gained sediment distilled water and dehydrated alcohol 3 times respectively, is placed in 120 DEG C of baking ovens Middle dry 3h, finally calcines 4h in 450 DEG C of air in muffle furnace, obtains Ni-MNC atom level site catalysts.
4th step extracts Ni-MNC atom level site catalysts, makes the Ni atom high point on carbon carrier It dissipates, comprising the following steps:
It is 5wt%'s that the atom level site catalysts that third step obtains, which are dispersed in 40ml Solute mass fraction, KClO3The second dispersion liquid is formed in solution, adjusts the second dispersion liquid pH < 7 with sodium carbonate liquor, so that the Ni of supported on carriers is former Son reaches maximum leaching content, is subsequently placed in 120 DEG C of oil bath pans and extracts 13h, until leaching liquor is all evaporated, is washed with distilled water It filters sediment 4 times, dry 12h, finally calcines 4h at 600 DEG C, obtain the Ni-MNC atom level of high degree of dispersion at 120 DEG C Site catalysts.
Progress ozone oxygen in fixed-bed reactor is placed in the Ni-MNC atom level site catalysts of above-mentioned preparation Catalyst is put into the quartz ampoule that internal diameter is 8mm and tests by the catalytic performance test for changing degradation methanol, toluene, and catalysis is anti- The length for answering device is 30cm, initial concentration and reaction using the gas chromatograph on-line checking VOCs equipped with fid detector Concentration afterwards uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control is as follows: VOCs initial concentration is 100~500mgm-3, ozone inlet concentration is 800mgm-3, reaction temperature is 25 DEG C, and gas reaction air speed is 9000h-1。 The results are shown in Table 6 for the catalytic performance test of Ni-MNC atom level site catalysts.
The catalytic performance test result of 6 Ni-MNC atom level site catalysts of table
Average degradation rate of the catalyst sample in embodiment to methanol, toluene, acetoneand ethyl acetate is aggregated into table 7 In.
Each atom level site catalysts catalytic performance test of table 7 compares
As can be seen from Table 7, the monoblock type N doping mesoporous carbon atom level of transition metal load provided by the invention is living Property site catalyst for methanol, toluene constant temperature catalyzing degradation all have preferable removal effect, degradation rate reach 90% with On.In addition, the monoblock type N doping mesoporous carbon atom level active site compared to the base metal load in embodiment 4~6 is urged Agent, the load of noble metal makes catalyst have a higher catalytic activity in Examples 1 to 3, to the degradation rate of VOCs under room temperature 95% or more can be reached.

Claims (6)

1. a kind of preparation method of the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal, special Sign be the following steps are included:
(1) chemical vapour deposition technique synthesizes CNTs:
The first step, by γ-Al2O3It pulverizes and sieves, retains the system that the part that diameter is 80~150 μm is used for CNTs growth catalyst It is standby；
Second step weighs the γ-Al that 5~10g is filtered out2O3It is immersed in the Fe that 50~100ml mass fraction is 60%~70% (NO3)3In solution, at 20~30 DEG C keep 12~for 24 hours；Then dry 20~30h in 90~120 DEG C of baking oven, then 2~4h is calcined in 350~450 DEG C of air, by Fe (NO3)3It is converted to Fe2O3, obtain Fe2O3/γ-Al2O3Precursor；
Third step, by the Fe2O3/γ-Al2O3Precursor is placed in tube furnace, first at 20~30 DEG C in flow be 180~ 200ml·min-1H220~40min is kept in air-flow, then rises to 400~650 with the heating rate of 10~20 DEG C/min DEG C, reductase 12~3h；Finally, temperature is risen to 750~950 DEG C with the heating rate of 10~20 DEG C/min, and use C2H6And H2 Flow is 50mlmin-1It or is 60mlmin-1Mixed gas replace H2, keep 2~3h to grow CNTs, obtain CNTs crude product；
The CNTs crude product is placed in 200~300ml aqueous slkali by the 4th step, it is heated at reflux 20 at 80~150 DEG C~ 30h, to remove γ-Al2O3Carrier, and for several times with distilled water filtering and washing, until cleaning solution is in neutrality；It is subsequently placed in 200~ In the acid solution of 300ml, it is heated at reflux 10~20h at 80~150 DEG C, to remove remaining metal impurities, and uses distilled water Filtering and washing for several times, until cleaning solution is in neutrality；Finally, the first sediment is placed in 100~200 DEG C of baking ovens, dry 20~ 30h obtains CNTs after purification；
(2) cryochemistry fusion method prepares monoblock type N doping mesoporous carbon:
Purifying CNTs, the 4~5g for taking 1~2g step (1) to obtain analyze pure solid glucose and 6~7g analyzes pure solid citric acid It is uniformly mixed, 2~3g ammonium carbonate powder is added, mixing is placed in 100~150 DEG C of baking oven dry 4~6h, is subsequently placed in pipe In formula furnace, with 2~3 DEG C of min-1Rate be warming up to 350~450 DEG C, in air calcine 3~4h, finally with 5~6 DEG C min-1Rate be warming up to 700~900 DEG C, in He gas anneal 2~4h, obtain monoblock type N doping mesoporous carbon；
(3) infusion process prepares atom level site catalysts:
The first step weighs the monoblock type N doping mesoporous carbon that 2~5g step (2) obtains and is distributed in 20~50ml distilled water, adds The salt or acid solution for entering transition metal, form the first dispersion liquid after mixing, transition metal and N doping in the first dispersion liquid is made to be situated between The mass ratio of hole carbon is 1:20~1:200；
The sodium borohydride of 0.1~0.5mol/L is added in second step, first dispersion liquid 30~40min of ultrasound that the first step is obtained Or 10~30ml of solution of potassium borohydride, and be vigorously stirred, until not generating H2, it is reduced metal ion；Then sodium carbonate is used It is 7~8 that solution, which adjusts pH value of solution, and magnetic agitation heats 3~5h at 60~120 DEG C, until moisture is all evaporated, gained at this time In second sediment in transition metal active atom uniform load to the mesoporous carbon carrier of N doping；
The second sediment distilled water and dehydrated alcohol are washed 3~4 times respectively and remove remaining Na by third step+Or K+, be subsequently placed in 80~150 DEG C of baking ovens dry 2~6h, finally in muffle furnace in 350~650 DEG C of air calcining 3~ 4h obtains atom level site catalysts；
4th step extracts atom level site catalysts, makes the metallic atom high degree of dispersion on carbon carrier, including with Lower step:
The atom level site catalysts that third step obtains are dispersed in 20~50ml leaching liquor and form the second dispersion liquid, are used Sodium carbonate liquor adjusts the second dispersion liquid pH value and the metallic atom of supported on carriers is made to reach maximum leaching content, is subsequently placed in 50 10~20h is extracted in~150 DEG C of oil bath pans, until leaching liquor is all evaporated, is washed with distilled water and is filtered third sediment 3~4 Secondary, dry 6~15h, finally calcines 2~5h at 350~650 DEG C at 80~150 DEG C, and the noble metal for obtaining high degree of dispersion is former Sub- grade site catalysts.
2. the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal according to claim 1 Preparation method, it is characterised in that: aqueous slkali in the 4th step is one of KOH solution or NaOH solution, is rubbed Your concentration is 1~2molL-1；The acid solution is one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetum, quality point Number is 20~70%.
3. the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal according to claim 1 Preparation method, it is characterised in that: the salt or acid solution of the transition metal in the step (3) be H2PtCl6、PdSO4、 HAuCl4、AgNO3、RuCl3、Rh(NO3)3、OsCl3、H2IrCl6、FeCl3、Co(NO3)2、Ni(NO3)2Or Cu (NO3)2In It is a kind of.
4. the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal according to claim 1 Preparation method, it is characterised in that: the leaching liquor be NaCN solution, KCN solution, NaClO3Solution, KClO3Solution, Mg (ClO3)2One of solution or thiourea solution, the Solute mass fraction of leaching liquor are 1~10wt%.
5. the monoblock type N doping mesoporous carbon atom level site catalysts of carrying transition metal according to claim 4 Preparation method, it is characterised in that: the Solute mass fraction of the leaching liquor be 2wt%.
6. according to the monoblock type N doping mesoporous carbon atom level active site of carrying transition metal described in claim 4 or 5 The preparation method of catalyst, it is characterised in that: when using NaCN solution or KCN solution as leaching liquor, adjust the second dispersion Liquid pH is 11~12；Make NaClO3Solution, KClO3Solution or Mg (ClO3)2When as leaching liquor, the second dispersion liquid pH of adjusting < 7；When using thiourea solution as leaching liquor, the second dispersion liquid pH > 7 are adjusted.
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