CN104772145B - Supported urushibara nickel catalyst and preparation method thereof - Google Patents
Supported urushibara nickel catalyst and preparation method thereof Download PDFInfo
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- CN104772145B CN104772145B CN201510142502.2A CN201510142502A CN104772145B CN 104772145 B CN104772145 B CN 104772145B CN 201510142502 A CN201510142502 A CN 201510142502A CN 104772145 B CN104772145 B CN 104772145B
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Abstract
A supported urushibara nickel catalyst is characterized in that the catalyst adopts ceramic as a supporter, SiO2 as a coat and metallic zinc and nickel as active components, the mass of the coat SiO2 is 10-20wt% of the mass of the coat supported supporter, the support amount of the active component Zn is 2-5wt% of the mass of the coat supported supporter, and the support amount of the active component Ni is 3-8wt% of the mass of the coat supported supporter. The catalyst is suitable for bubble reactors, and has the advantages of simple separation, high mechanical strength and large specific surface area.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method thereof, particularly relates to a kind of monoblock type Uru shibara nickel catalyst
And preparation method thereof.
Background technology
Toluenediamine is a kind of important organic chemistry raw material, is commonly used to synthesize toluene di-isocyanate(TDI) (TDI).At present,
The catalyst of industrial catalysis hydrogenation of dinitro toluene synthesis toluenediamine is mainly loaded noble metal catalyst and skeleton nickel
Catalyst, carried noble metal is then expensive and easy coking deactivation, and skeletal nickel catalyst has easy spontaneous combustion and environmental pollution is tight
The problems such as weight.
Uru shibara nickel catalyst is to adopt reduction Zn powder substitution Ni in nineteen fifty-two by scientist's paint is former2+For simple substance Ni, using alkali
Liquid activation is prepared.Uru shibara nickel catalyst preparation process is simple, is difficult spontaneous combustion, and has good settleability, can be numerous
The catalytic performance similar to skeletal nickel catalyst is shown in hydrogenation reaction.But Uru shibara nickel catalyst specific surface area is little, easily roll into a ball
Poly- inactivation, constrains its process of industrialization.
Patent CN102744071A discloses a kind of preparation method of load Uru shibara nickel catalyst, it is characterised in that first will
SiO after soluble ferric iron salt and dried process2Or γ-Al2O3Carrier is impregnated, and Fe is obtained with after calcination process being dried2O3/
SiO2Or Fe2O3/γ-Al2O3Presoma, then carries out hydrogen reduction process by precursor, the Fe/SiO that reduction is obtained2Or Fe/
γ-Al2O3Reacted with soluble nickel salt and auxiliary agent, be precipitated the suspension of nickel and auxiliary agent, scrubbed, sour expansion etc.
Support type Uru shibara nickel catalyst is obtained after process.Although the method realizes the load of lacquer original nickel, but replaces Zn to make reducing agent with Fe
After there are problems that catalyst preparation time length and Ni dispersion.
Patent CN103272605A discloses a kind of method that employing sol-gal process prepares support type lacquer original nickel, its feature
It is to configure soluble nickel salt first to mix with the mixed solution of auxiliary agent and the suspension of Zn powder and by the two, reaction is sunk
The suspension of shallow lake nickel, then obtains Ludox, by the suspension of coprecipitated nickel hydroxide with Ludox additional by processing tetraethyl orthosilicate
Plastic is stirred under the conditions of glacial acetic acid, gel is in N2Middle roasting obtains finished catalyst.The method is anti-using zinc powder reduction nickel ion
Speed is answered, but has stronger heat release during the course of the reaction and with the consumption of part water, large effect plastic process,
It is unfavorable for the control of catalyst crystallite dimension.Patent CN103341361A discloses one kind and prepares support type lacquer original nickel using plating
Method, it is characterised in that with porous material as negative electrode, zinc bar is anode, and with galvanoplastic support type Zn presomas are prepared,
It is dispersed in water after the presoma washing is ground and is reacted with nickel salt, gained suspension obtains support type paint Jing after acid activation
Former Raney nickel.The method solves the problems, such as the difficult loads of Zn, but the zinc that is supported on carrier using plating is dense and exists
The uneven problem of plating, is unfavorable for further reducing nickel ion, so as to influence whether the composition of catalyst activity component.
It is more uniform that integral catalyzer can promote reactant to be distributed in catalyst particle surface, can strengthen chemical mistake
Journey, forms the new technology of more compact, cleaning and energy-conservation, the great development potentiality in heterogeneous catalysis field.Patent
CN1245163A discloses a kind of improved method for hydrogenation of dinitro toluene, and it in plug flow reactor system by mixing
Enter integer catalyzer, enable dinitrotoluene (DNT) it is continuous, substantially solvent-freely, insulation hydrogen addition generates toluenediamine, but reacts and stop
Time is short, and course of reaction control is complicated.
The content of the invention
It is applied to bubbling style reactor it is an object of the present invention to provide a kind of, and with high mechanical properties and bigger serface
Support type Uru shibara nickel catalyst and preparation method.
Ceramics of the present invention are carrier, with SiO2For coating, metallic zinc and nickel are active component, and catalyst is consisted of：
Coating SiO2Quality is the 10-20wt% for loading carrier after coating, and active component Zn load capacity is the 2- for loading carrier after coating
5wt%, active component Ni load capacity is the 3-8wt% for loading carrier after coating.
The preparation method of catalyst of the present invention is：
(1) ceramic monolith is soaked into 1-3min in coating paste, is purged with air after taking-up, at dry and roasting
Reason, makes coating be attached on ceramic monolith, obtains carrier after coating；
(2) coated carrier is put in vacuum chamber, backward vacuum chamber in be filled with quality be coated carrier 1%-3% Zn
(CH3)2, 130-140Pa is evacuated down to after 1-3min, scan 4- in carrier surface with the ultraviolet continuous argon ion of frequency multiplication
9min, then to vacuum chamber the Zn (CH that quality is coated carrier 5%-12% are filled with3)2, with defocused impulse quasi-molecule ArF laser
Irradiation 60-90s, Zn is carried on carrier coating；
(3) carrier for having loaded Zn in step (2) is immersed in the nickel salt solution for having configured, at 60-80 DEG C 1- is reacted
3h, activates finished catalyst needed for 0.5-2h is both obtained with acetic acid under identical temperature conditionss afterwards.
Ceramic monolith described in step (1) is that (6 × 8-12cm of Φ, hole density is 240- to cordierite honeycomb ceramics
280cpsi, unit weight 0.5-0.7g/cm3)。
Coating paste described in step (1) is Ludox, wherein, the solid content of Ludox slurry be 20-40wt% (admittedly contain
Amount=non-volatile part content/total amount × 100%), coating paste temperature is controlled for 50-60 DEG C.
The ceramic monolith treatment conditions after coating are loaded in step (1) is：300-500 DEG C of sintering temperature, roasting time
1-3h.
Argon ion laser control condition is in step (2)：λ=250-257nm, P=0.010-3.000mw.
Quasi-molecule ArF laser irradiation control conditions are in step (2)：λ=190-195nm, 10-12mJ/ pulse, 8-
10ns。
Nickel salt described in step (3) is nickel chloride, nickel nitrate or nickel acetate, and configuration concentration is 0.25-1mol/L, load
When in the carrier immersion nickel salt solution of Zn, Zn is controlled:Ni mass ratioes are 1-4:1.
Acetic acid concentration is 1-3mol/L in step (3), and the mole for adding acetic acid is 1-3 times of Zn moles.
The present invention it is a technical advantage that：
(1) catalyst that the present invention is provided is conducive to being uniformly distributed for vapour-liquid, can promote reactant in catalyst granules table
EDS maps are uniform, improve catalytic reaction efficiency, optimize course of reaction；
(2) catalyst that the present invention is provided has outstanding heat resisting performance, and strong mechanical strength is anti-in bubble type
Answer and there is longer service life in device and there is no the separation problem of catalyst fines；
(3) catalyst SiO of the present invention2Coating can provide higher specific surface area, there is preferable high temperature resistant and chemically-resistant
Corrosivity, can be such that catalyst activity component is effectively securely joined with carrier, be conducive to the dispersed of active component；
(4) catalyst loading process of the present invention is made the decomposition of source gas molecule due to the excitation of light, is adsorbed and anti-
Dynamic process should be waited to accelerate, so as to improve the speed under load of active component, shorten load time and active component and load
The adhesion of body is higher；
(5) present invention load uses laser induced chemical vapor depostion method, on the one hand solves the problems, such as the difficult loads of Zn, the opposing party
The Zn of face load it is more uniform and during avoid contact with foreign substance, it is ensured that final prepared catalyst it is pure
Property.
Specific embodiment
With reference to specific embodiment, this kind of support type Uru shibara nickel catalyst and preparation method thereof is further illustrated, while
Provide its reaction test result to describe its catalytic performance, but the invention is not limited in these embodiments.
Embodiment 1
(1) by 6 × 10cm of Φ, hole density is 260cpsi, unit weight 0.6g/cm3Ceramic monolith immerse 55 DEG C of solid contents be
In 30% Ludox and it is stirred continuously, is slowly withdrawn after 2min and is purged with air, 1h, Zhi Houfang is dried at 110 DEG C
Enter 300 DEG C of roasting 3h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 2% Zn
(CH3)2, 130Pa is evacuated down to after 1min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=250nm, P=3.000mw)
After body surface Surface scan 4min, to vacuum chamber the Zn (CH that quality is coated carrier 7% are filled with3)2, swashed with defocused impulse quasi-molecule ArF
Light (λ=195nm, 12mJ/ pulse, 10ns) irradiation 60s, Zn is carried on carrier coating；
(3) nickel chloride solution of 300ml 0.5mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into configuration
1h is reacted under 80 DEG C of stirring in water bath in solution, required finished product had both been obtained with 300mL 1mol/L acetic acid activation 30min afterwards and has been urged
Agent.Catalyst is consisted of：Coating SiO2Quality is the 15wt% for loading carrier after coating, active component Zn and Ni load capacity point
The 3wt% and 4wt% of carrier after coating Wei not loaded.
(4) catalyst performance evaluation：The catalyst for preparing with the reaction of DNT hydrogenation synthesis TDA as probe, continuous
Evaluated in bubbling style reactor.It is initial that 10g DNT are dissolved in into 200ml methyl alcohol and the bubbling equipped with integer catalyzer is added
In formula reactor, with nitrogen punching press and 30min is maintained, be subsequently passed hydrogen in 110 DEG C, reacted under 2MPa.Liquid phase feeding
1.6ml/min, gas space velocity 10h-1.Using its thing phase composition of GC-9160 types gas chromatographic analysis after reactor product is stable, analysis
As a result 1 is seen attached list.
Embodiment 2
(1) by 6 × 10cm of Φ, hole density is 260cpsi, unit weight 0.6g/cm3Ceramic monolith immerse 55 DEG C of solid contents be
In 30% silica gel and it is stirred continuously, is slowly withdrawn after 3min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
500 DEG C of roasting 1h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 2% Zn
(CH3)2, 140Pa is evacuated down to after 3min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=255nm, P=2.500mw)
After body surface Surface scan 6min, to vacuum chamber the Zn (CH that quality is coated carrier 9% are filled with3)2, swashed with defocused impulse quasi-molecule ArF
Light (λ=192nm, 10mJ/ pulse, 10ns) irradiation 70s, Zn is carried on carrier coating；
(3) nickel chloride solution of 300ml 0.75mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into configuration
Solution in 1h is reacted under 70 DEG C of stirring in water bath, both obtained the catalysis of required finished product with 300mL 2mol/L acetic acid activation 1h afterwards
Agent.Catalyst is consisted of：Coating SiO2Quality is the 16wt% for loading carrier after coating, and active component Zn and Ni load capacity are distinguished
The 3wt% and 5wt% of carrier after to load coating.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Embodiment 3
(1) by 6 × 10cm of Φ, hole density is 260cpsi, unit weight 0.6g/cm3Ceramic monolith immerse 55 DEG C of solid contents be
In 30% silica gel and it is stirred continuously, is slowly withdrawn after 2min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
400 DEG C of roasting 2h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 2% Zn
(CH3)2, 135Pa is evacuated down to after 1min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=257nm, P=2.000mw)
After body surface Surface scan 7min, to vacuum chamber the Zn (CH that quality is coated carrier 12% are filled with3)2, with defocused impulse quasi-molecule ArF
Laser (λ=195nm, 11mJ/ pulse, 8ns) irradiation 70s, Zn is carried on carrier coating；
(3) nickel chloride solution of 300ml 1mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into the molten of configuration
2h is reacted under 80 DEG C of stirring in water bath in liquid, required finished product catalysis had both been obtained with 300mL 3mol/L acetic acid activation 2.5h afterwards
Agent.Catalyst is consisted of：Coating SiO2Quality is the 15wt% for loading carrier after coating, and active component Zn and Ni load capacity are distinguished
The 4wt% and 7wt% of carrier after to load coating.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Embodiment 4
(1) by 6 × 12cm of Φ, hole density is 240cpsi, unit weight 0.5g/cm3Ceramic monolith immerse 60 DEG C of solid contents be
In 40% silica gel and it is stirred continuously, is slowly withdrawn after 1min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
400 DEG C of roasting 2h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 3% Zn
(CH3)2, 140Pa is evacuated down to after 2min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=251nm, P=0.900mw)
After body surface Surface scan 9min, to vacuum chamber the Zn (CH that quality is coated carrier 10% are filled with3)2, with defocused impulse quasi-molecule ArF
Laser (λ=192nm, 10mJ/ pulse, 8ns) irradiation 80s, Zn is carried on carrier coating；
(3) nickel chloride solution of 300ml 0.75mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into configuration
Solution in 3h is reacted under 60 DEG C of stirring in water bath, both obtained required finished product and urged with 300mL 2mol/L acetic acid activation 1.5h afterwards
Agent.Catalyst is consisted of：Coating SiO2Quality is the 18wt% for loading carrier after coating, active component Zn and Ni load capacity point
The 4wt% and 5wt% of carrier after coating Wei not loaded.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Embodiment 5
(1) by 6 × 12cm of Φ, hole density is 240cpsi, unit weight 0.5g/cm3Ceramic monolith immerse 60 DEG C of solid contents be
In 40% silica gel and it is stirred continuously, is slowly withdrawn after 2min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
500 DEG C of roasting 1h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 3% Zn
(CH3)2, 135Pa is evacuated down to after 3min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=257nm, P=1.500mw)
After body surface Surface scan 5min, to vacuum chamber the Zn (CH that quality is coated carrier 12% are filled with3)2, with defocused impulse quasi-molecule ArF
Laser (λ=190nm, 10mJ/ pulse, 8ns) irradiation 90s, Zn is carried on carrier coating；
(3) nickel chloride solution of 300ml 1mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into the molten of configuration
2h is reacted under 70 DEG C of stirring in water bath in liquid, required finished catalyst had both been obtained with 300mL 3mol/L acetic acid activation 1h afterwards.
Catalyst is consisted of：Coating SiO2Quality is the 19wt% for loading carrier after coating, and active component Zn and Ni load capacity are respectively
The 5wt% and 7wt% of carrier after load coating.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Embodiment 6
(1) by 6 × 8cm of Φ, hole density is 280cpsi, unit weight 0.7g/cm3Ceramic monolith immerse 50 DEG C of solid contents be
In 20% silica gel and it is stirred continuously, is slowly withdrawn after 3min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
300 DEG C of roasting 2h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 1% Zn
(CH3)2, 135Pa is evacuated down to after 1min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=256nm, P=2.500mw)
After body surface Surface scan 7min, to vacuum chamber the Zn (CH that quality is coated carrier 8% are filled with3)2, swashed with defocused impulse quasi-molecule ArF
Light (λ=195nm, 12mJ/ pulse, 8ns) irradiation 80s, Zn is carried on carrier coating；
(3) nickel acetate solution of 300ml 0.75mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into configuration
Solution in 2h is reacted under 60 DEG C of stirring in water bath, both obtained the catalysis of required finished product with 400mL 2mol/L acetic acid activation 2h afterwards
Agent.Catalyst is consisted of：Coating SiO2Quality is the 12wt% for loading carrier after coating, and active component Zn and Ni load capacity are distinguished
The 2wt% and 6wt% of carrier after to load coating.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Embodiment 7
(1) by 6 × 8cm of Φ, hole density is 280cpsi, unit weight 0.7g/cm3Ceramic monolith immerse 50 DEG C of solid contents be
In 20% silica gel and it is stirred continuously, is slowly withdrawn after 2min and is purged with air, 1h is dried at 110 DEG C, is put into afterwards
500 DEG C of roasting 2h of Muffle furnace, obtain carrier after coating；
(2) carrier after coating is put in vacuum chamber, backward vacuum chamber be filled with quality be coated carrier 1% Zn
(CH3)2, 130Pa is evacuated down to after 1min.Carried with the ultraviolet continuous argon ion of frequency multiplication (λ=254nm, P=2.000mw)
After body surface Surface scan 4min, to vacuum chamber the Zn (CH that quality is coated carrier 10% are filled with3)2, with defocused impulse quasi-molecule ArF
Laser (λ=194nm, 12mJ/ pulse, 10ns) irradiation 85s, Zn is carried on carrier coating；
(3) nickel nitrate solution of 300ml 0.75mol/L is configured, the carrier for having loaded Zn in step (2) is immersed into configuration
Solution in 1h is reacted under 80 DEG C of stirring in water bath, afterwards with 300mL 3mol/L acetic acid activation 30min both obtained required finished product
Catalyst.Catalyst is consisted of：Coating SiO2Quality is the 10wt% for loading carrier after coating, active component Zn and Ni load capacity
Respectively load the 3wt% and 6wt% of carrier after coating.
(4) catalyst performance evaluation：With embodiment 1, analysis result sees attached list 1 to evaluation method.
Subordinate list 1
Claims (9)
1. a kind of support type Uru shibara nickel catalyst, it is characterised in that ceramics are carrier, with SiO2For coating, metallic zinc and nickel are to live
Property component, catalyst consists of coating SiO2Quality is the 10-20 wt% for loading carrier after coating, and active component Zn load capacity is
The 2-5wt% of carrier after load coating, active component Ni load capacity is the 3-8wt% for loading carrier after coating；
And prepare by the following method：
(1) ceramic monolith is soaked into 1-3min in coating paste, is purged with air after taking-up, through dry and calcination process,
Coating is attached on ceramic monolith, obtain carrier after coating；
(2) coated carrier is put in vacuum chamber, backward vacuum chamber in be filled with quality be coated carrier 1%-3% Zn (CH3)2,
130-140Pa is evacuated down to after 1-3min, 4-9min is scanned in carrier surface with the ultraviolet continuous argon ion of frequency multiplication, subsequently
Zn (the CH that quality is coated carrier 5%-12% are filled with to vacuum chamber3)2, with defocused impulse quasi-molecule ArF laser irradiation 60-90s,
Zn is carried on carrier coating；
(3) carrier for having loaded Zn in step (2) is immersed in the nickel salt solution for having configured, at 60-80 DEG C 1-3h is reacted, it
Afterwards 0.5-2h is activated under identical temperature conditionss with acetic acid and obtain final product required finished catalyst.
2. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that ceramic monolith described in step (1)
It is 6 × 8-12cm of Φ for cordierite honeycomb ceramics, hole density is 240-280cpsi, unit weight 0.5-0.7g/cm3。
3. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that coating paste described in step (1)
For Ludox, wherein, the solid content of Ludox slurry is 20-40wt%, and it is 50-60 DEG C control coating paste temperature.
4. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that in step (1) after load coating
Ceramic monolith roasting condition is：300-500 DEG C of sintering temperature, roasting time 1-3h.
5. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that frequency multiplication is ultraviolet continuous in step (2)
Argon ion laser control condition is：λ=250-257nm, P=0.010-3.000 mw.
6. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that accurate point of defocused impulse in step (2)
Sub- ArF laser irradiation control condition is：λ=190-195nm, 10-12mJ/ pulse, 8-10 ns.
7. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that nickel salt described in step (3) is chlorine
Change nickel, nickel nitrate or nickel acetate, configuration concentration is 0.25-1mol/L.
8. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that the carrier of load Zn in step (3)
When in immersion nickel salt solution, Zn is controlled:Ni mass ratioes are 1-4:1.
9. a kind of support type Uru shibara nickel catalyst as claimed in claim 1, it is characterised in that acetic acid concentration is in step (3)
1-3mol/L, the mole for adding acetic acid is 1-3 times of Zn moles.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161339A (en) * | 2007-11-28 | 2008-04-16 | 南开大学 | Application of Chinese lacquer original nickel in the preparation of m-phenylene diamine with m-dinitrobenzene liquid phase hydrogenation |
| CN103272605A (en) * | 2013-06-04 | 2013-09-04 | 太原理工大学 | Supported paint U-Ni-A catalyst and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9573965B2 (en) * | 2013-02-19 | 2017-02-21 | Aurobindo Pharma Ltd | Process for the preparation of Dolutegravir |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161339A (en) * | 2007-11-28 | 2008-04-16 | 南开大学 | Application of Chinese lacquer original nickel in the preparation of m-phenylene diamine with m-dinitrobenzene liquid phase hydrogenation |
| CN103272605A (en) * | 2013-06-04 | 2013-09-04 | 太原理工大学 | Supported paint U-Ni-A catalyst and preparation process thereof |
Non-Patent Citations (3)
| Title |
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| ZnO synthesis by high vacuum plasma-assisted chemical vapor deposition using dimethylzinc and atomic oxygen;Teresa M. Barnes等;《J. Vac. Sci. Technol. A》;20040924;第22卷(第5期);第2118-2125页 * |
| 原位沉淀技术制备整体型Mn/Ti-Si/堇青石选择性催化还原催化剂;黄海凤等;《中国电机工程学报》;20110615;第31卷(第17期);第50-54页 * |
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