CN105148939B - A kind of high-dispersion loading type PtCo nanometer alloy catalysts and its preparation method and application - Google Patents
A kind of high-dispersion loading type PtCo nanometer alloy catalysts and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of high-dispersion loading type PtCo nanometer alloy catalysts and its preparation method and application.The present invention is mixed noble metal precursor, Mg Al Co layered double hydroxide precursors with melamine by simple concurrent roasting, and then a step is simultaneously compound under the high temperature conditions and reduces, and finally gives carbonitride (C3N4) load high dispersive PtCo nanometer alloy catalysts.Be applied in the reaction that cinnamic acid selective hydrogenation prepares fragrant cinnamyl alcohol, the conversion ratio of cinnamic acid and to cinnamyl alcohol selectivity respectively up to 85~100% and 80~100%.High-dispersion loading type PtCo nanometer alloy catalyst preparation method environmental protections, structure novel and unique, and catalyst stability are strong, thus are with a wide range of applications.
Description
Technical field
The present invention relates to catalyst preparation technical field, and in particular to a kind of support type PtCo nanometer alloy catalysts and its
Preparation method.The catalyst is used for the selective hydrogenation of cinnamic acid.
Technical background
α, beta-unsaturated aldehyde ketone has conjugated bonds (C=C and C=O keys), there is C=C double bonds in hydrogenation reaction and C=O is double
Key competitive Adsorption is acted on, so that selective hydrogenation has the product of different selective hydrogenations.Cinnamic acid is alpha, beta-unsaturated aldehyde
The representative species of ketone, its selection hydrogenation products are all widely used in spices, medicine and other fields, such as cinnamyl alcohol.Make extensively at present
Hydrogenation on cinnamic aldehyde catalyst is Pt catalyst, but activity and selectivity of the monometallic Pt catalyst in hydrogenation reaction is simultaneously
Non-optimal.Bimetallic (alloy) catalyst usually has electronic structure and the chemical property dramatically different compared to monometallic
([Xueqin Wang,Gongliang Li,Umit S.Ozkan.J.Mol.Catal.A:2004,217:219–229]
[Lihong Zhao, Kegong Fang, Dong Jiang.Catal.Today.2010,158,490-495]) so as to prepare
High performance catalyst provides chance.
In document Hao Cheng, Guangwen ChenDiyong Wu Shudong Wang, Yin Zhang,
Henqiang Li.Korean Journal of Chemical Engineering, Cheng systems in 2004,21,595-600.
For single-metal reforming catalyst Pt/Mg (Al) O.With Al2O3Carrier is compared, phase interaction of houghite carrier Mg (Al) between O and Pt
With stronger.Carrier Mg (Al) O of this alkalescence makes catalyst Pt/Mg (Al) O have unique advantageous property.But party's legal system
Standby process is complicated, and has chronic murder by poisoning using the toluene used in preparation process.
In document Yan li, Zhen Guo Li.J.M.Catal.A:2008,279:In 140-146, using dipping legal system
For the PtCo bimetallic catalysts with CNTs as carrier.Its preparation method be by Pt, Co metal impregnation on CNTs, be used in combination
KBH4Reduction.The catalyst is used in cinnamic acid selection and is hydrogenated to cinnamyl alcohol, selects the conversion ratio of hydrogenation there was only 85.9%.Cause
A kind of this method for preparing catalyst of green high-efficient of research has very big realistic meaning.
Layered double hydroxide (LDHs) is by the change of interlayer anion and positively charged laminate ordered fabrication
Compound.LDHs chemical constitution formulas are [M2+ 1-xM3+ x(OH)2](An- x/n)·mH2O, wherein M2+And M3+Divalence and trivalent are represented respectively
Metal cation, in main layer board；An-It is interlayer anion.The layer structure of LDHs makes it have peculiar property, such as layer
Plate constitutes adjustable denaturation, interlayer anion interchangeability and acid and basic character etc..Due to the flexibility of its structure, in recent years
Carrying out LDHs has turned into the important materials for preparing various catalyst, catalyst precarsor, catalyst carrier.
The content of the invention
It is an object of the present invention to provide a kind of high-dispersion loading type nano Pt/C o alloy catalysts and preparation method thereof, and will
It is used for selective hydrogenation cinnamic acid and prepares cinnamyl alcohol.
The high-dispersion loading type nano Pt/C o alloy catalysts that the present invention is provided, chemical representation is：PtCo/MMO-C3N4。
Wherein MMO represents the metal oxide after roasting, is MgO and Al2O3, C3N4It is product, C after melamine roasting3N4It is with MMO
The complex carrier of catalyst；The average grain diameter of PtCo Nanoalloys particle is 3~10nm, the weight/mass percentage composition of Pt in catalyst
The weight/mass percentage composition for being 2.0~5.5%, Co is 0.5~2.5%；Conversion ratio of the catalyst in the hydrogenation reaction of cinnamic acid
It is that the selectivity that 85~100%, C=O keys are hydrogenated to cinnamyl alcohol is 80~100%.
The preparation scheme of above-mentioned catalyst is：The magnalium hydrotalcite of the cobalt intercalation for first preparing, by the hydrotalcite and chloroplatinic acid
Sodium and melamine mix, and platinic sodium chloride, the magnalium hydrotalcite of cobalt intercalation and melamine are combined under the high temperature conditions, obtain
PtCo/MMO-C3N4Catalyst.
The preparation method of the high-dispersion loading type PtCo nanometer alloy catalysts that the present invention is provided, comprises the following steps that：
A. the mixing salt solution containing magnesium nitrate, aluminum nitrate and cobalt nitrate is prepared with deionized water, and makes wherein magnesium nitrate
Concentration is 0.03~0.10mol/L, and the concentration of aluminum nitrate is 0.03~0.10mol/L, and the concentration of cobalt nitrate is 0~2.0mmol/
L；Wherein, magnesium nitrate and the molar concentration rate of aluminum nitrate are 1~3:1；The LiOH alkali of 0.1~0.3mol/L is prepared with deionized water
Property solution；
B. mixing salt solution in step A is titrated with LiOH aqueous slkalis, the pH value to mixing salt solution is 7~11,
6~24h of crystallization at a temperature of 70~90 DEG C, is cooled to room temperature, filtering, is washed with deionized to neutrality, is dried at 70 DEG C,
Obtain the magnalium hydrotalcite precipitation of cobalt intercalation；
The magnalium hydrotalcite precipitation of the cobalt intercalation that C. step B is obtained mixes with platinic sodium chloride and melamine, makes mixing
The mol ratio of platinic sodium chloride/magnesium nitrate is 1 in thing：30~70, the mol ratio of melamine/magnesium nitrate is 1:1, mixture is in nitrogen
450~600 DEG C are heated under gas atmosphere, 3~6h is kept；Room temperature is naturally cooled to, that is, obtains high-dispersion loading type nano Pt/C o
Alloy catalyst PtCo/MMO-C3N4。
The characteristics of this method is that, without additional reducing agent, in the high-temperature calcination process of step C, melamine act as
C3N4The precursor of carrier, the C of formation3N4Carrier itself has gentle reproducibility, by Pt Co metal ion in-situ reducings
Into PtCo alloys.The MMO-C for being formed simultaneously3N4Carrier has high-specific surface area, is conducive to dispersion alloy nano-particle；And carry
Strong interaction between body and nano-particle can improve the structural stability of catalyst.
High-dispersion loading type nano Pt/C o alloy catalysts to obtaining carry out structural characterization.Can be with by the electron microscope of Fig. 1
It was found that catalyst particle size is consistent to understand it is PtCo alloys according to lattice fringe.X-ray photoelectron power spectrum (XPS) result table of Fig. 2
Pt 3d electron binding energies occur combining the trend that energy direction is moved to height in bright catalyst, illustrate between active metal Pt and Co
In the presence of very strong interaction.
The catalyst that will be prepared is applied to liquid phase cinnamic acid selective hydrogenation and tests its catalytic performance, method be by
Cinnamic acid is dissolved in 50ml alcohol solvents, is configured to the cinnamic acid solution that concentration is 56mmol/L, then 0.02g load nanometers are closed
Au catalyst is added in autoclave, is passed through the H of 2.0MPa2, temperature rises to 80 DEG C of reactions, reacts 90min.Result is shown in figure
3, it is seen that up to 85~100%, catalyst is selectively 80~100% to cinnamyl alcohol to the conversion ratio of hydrogenation on cinnamic aldehyde reaction,
The present invention has following remarkable result：(1) support type PtCo alloy catalysts prepare simple, layered bi-metal hydrogen
Oxide is combined with melamine, is settled at one go without additional reducing agent.Preparation method green non-pollution.(2) in high-temperature roasting
During, the C in catalyst carrier3N4Itself have reproducibility, without additional reducing agent, can in-situ reducing Pt Co metals from
Son；(3) hydrotalcite after being calcined is conducive to dispersion alloy nano-particle, and strong interaction between carrier and nano-particle can
To improve the structural stability of catalyst；(4) high activity, polymolecularity based on loaded nano particle itself, this catalyst
Excellent catalytic performance is embodied in the hydrogenation reaction of cinnamic acid, has been 85~100% to cinnamic acid aldehyde conversion ratio, to Chinese cassia tree
The selectivity of alcohol is 80~100%, with potential actual application value.
Brief description of the drawings
Fig. 1 are PtCo/MMO-C prepared by embodiment 23N4Catalyst high power transmission electron microscope (HRTEM) figure.
Fig. 2 are PtCo/MMO-C prepared by embodiment 23N4Catalyst x-ray photoelectron power spectrum (XPS) figure.
Fig. 3 are PtCo/MMO-C prepared by embodiment 23N4Catalyst hydrogenation on cinnamic aldehyde conversion ratio and the selection to cinnamyl alcohol
Property time history plot.
Specific embodiment
Embodiment 1
By 1.536g Mg (NO3)2·6H2O, 1.125g Al (NO3)3·9H2O and 0.0173g Co (NO3)2·6H2O matches somebody with somebody
It is made 100ml mixing salt solutions, it is the LiOH solution of 0.1mol/L in above-mentioned mixed salt solution that concentration is added dropwise, and is adjusted molten
The pH=9.0 of liquid；Crystallization 24h under 70 DEG C of reaction temperatures；Room temperature is cooled to, with deionized water centrifuge washing to neutrality, at 70 DEG C
Lower drying, obtains MgAl-Co-LDH precipitations.
By 0.1235g MgAl-Co-LDH precipitations, 0.0883g Na2PtCl4·6H2O and 1.418g melamines mix,
500 DEG C are heated in a nitrogen atmosphere, 5h is kept, room temperature is naturally cooled to, that is, obtain high-dispersion loading type nano Pt/C o alloys
Catalyst.Wherein metal alloy nanoparticles average grain diameter is 5nm, and the weight/mass percentage composition of Pt elements is 4.6% in catalyst,
The weight/mass percentage composition of Co elements is 0.5% in catalyst.
Hydrogenation on cinnamic aldehyde catalytic reaction, first toward the reactant cinnamic acid for adding 0.2ml in autoclave simultaneously,
Catalyst and 100ml alcohol solvents that 0.02g steps C is obtained.Reaction unit is installed, is tightened, be passed through nitrogen and be put into 80 DEG C of oil
2h is preheated in bath.Finally release N2Gas, is passed through H2Gas to 2.0MPa, stirring starts reaction.When hydrogenation reaction proceeds to 90min,
The conversion ratio of cinnamic acid has reached 95%, and the selectivity to cinnamyl alcohol is 93%.
Embodiment 2
By 1.536g Mg (NO3)2·6H2O, 1.125g Al (NO3)3·9H2O and 0.04325g Co (NO3)2·6H2O matches somebody with somebody
It is made 100ml mixing salt solutions, it is the LiOH solution of 0.1mol/L in above-mentioned mixed salt solution that concentration is added dropwise, and is adjusted molten
The pH=9.0 of liquid；Crystallization 24h under 70 DEG C of reaction temperatures；Room temperature is cooled to, with deionized water centrifuge washing to neutrality, at 70 DEG C
Lower drying, obtains LDHs precipitations.By 0.1235g MgAl-Co-LDH, 0.0893g Na2PtCl4·6H2O and 1.418g melamines
Amine mixes, and 600 DEG C are heated in a nitrogen atmosphere, keeps 5h, naturally cools to room temperature, that is, obtain high-dispersion loading type nanometer
PtCo alloy catalysts.Wherein the average grain diameter of alloy is 7nm, and the weight/mass percentage composition of Pt elements is 4.7% in catalyst, is urged
The weight/mass percentage composition of Co elements is 1.0% in agent.
Hydrogenation on cinnamic aldehyde catalytic perfomance method of testing reaches with embodiment 1, the conversion ratio for measuring cinnamic acid
100%, the selectivity to cinnamyl alcohol is 100%.
Embodiment 3
By 1.536g Mg (NO3)2·6H2O, 1.125g Al (NO3)3·9H2O and 0.1068g Co (NO3)2·6H2O matches somebody with somebody
It is made 100ml mixing salt solutions, it is the LiOH solution of 0.1mol/L in above-mentioned mixed salt solution that concentration is added dropwise, and is adjusted molten
The pH=9.0 of liquid；Crystallization 24h under 70 DEG C of reaction temperatures；Room temperature is cooled to, with deionized water centrifuge washing to neutrality, at 70 DEG C
Lower drying, obtains MgAl-Co-LDH precipitations.By 0.1235g MgAl-Co-LDH, 0.0907g a2PtCl4·6H2O and three
1.418g poly cyanamids mix, and 600 DEG C are heated in a nitrogen atmosphere, keep 6h, naturally cool to room temperature, that is, obtain high dispersive and bear
Load type nano Pt/C o alloy catalysts.Wherein the average grain diameter of metal alloy nanoparticles is 9.5nm, Pt elements in catalyst
Weight/mass percentage composition is 5.0%, and the weight/mass percentage composition of Co elements is 1.5% in catalyst.
Hydrogenation on cinnamic aldehyde catalytic perfomance method of testing has reached 92% with embodiment 1, the conversion ratio for measuring cinnamic acid,
Selectivity to cinnamyl alcohol is 86%.
Comparative example
According to the composition of raw materials of embodiment 1, Co (NO are simply not added with3)2·6H2O prepares not cobalt-containing catalyst Pt/MMO-
C3N4。
By 1.536g Mg (NO3)2·6H2O and 1.125g Al (NO3)3·9H2O is configured to 100ml mixing salt solutions, drop
Plus concentration is the LiOH solution of 0.2mol/L in above-mentioned mixed salt solution, the pH=10.0 of solution is adjusted；80 DEG C of reactions
At a temperature of crystallization 12h；Room temperature is cooled to, with deionized water centrifuge washing to neutrality, is dried at 70 DEG C, obtained MgAl-LDH and sink
Form sediment.By 0.1235g MgAl-LDHs, 0.0879g Na2PtCl4·6H2O and 1.418g melamines mix, in a nitrogen atmosphere
500 DEG C are heated to, 3h is kept, room temperature is naturally cooled to, that is, obtain PtCo/MMO-C3N4Nanocatalyst.Wherein metallic nanoparticle
The average grain diameter of son is 4nm, and the weight/mass percentage composition of Pt elements is 5.0% in catalyst.
With embodiment 1, it is 86% to measure the conversion ratio of cinnamic acid to hydrogenation on cinnamic aldehyde catalytic perfomance method of testing, to meat
The selectivity of cinnamic alcohol is 82%.Far below catalyst prepared by embodiment 1-3.
Claims (3)
1. a kind of preparation method of high-dispersion loading type PtCo nanometer alloy catalysts, specific preparation process is as follows：
A. prepare the mixed solution containing magnesium nitrate, aluminum nitrate and cobalt nitrate with deionized water, and make the concentration of wherein magnesium nitrate be
0.03~0.10mol/L, the concentration of aluminum nitrate is 0.03~0.10mol/L, and the concentration of cobalt nitrate is 0~2.0mmol/L；Its
In, magnesium nitrate is 1 with the molar concentration rate of aluminum nitrate:1~3:1；The alkaline solution of LiOH is prepared with deionized water, LiOH's is dense
It is 0.1~0.3mol/L to spend；
B. the metal salt solution prepared in A methods is titrated with LiOH aqueous slkalis, it is 7~11 to control the pH value of solution,
6~24h of crystallization at a temperature of 70~90 DEG C, is cooled to room temperature, filtering, is washed with deionized to neutrality, is dried at 70 DEG C,
Obtain LDHs precipitations；
C. LDHs, platinic sodium chloride and melamine are mixed, wherein the mol ratio of platinic sodium chloride/magnesium nitrate is 1：30~70, three
The mol ratio of poly cyanamid/magnesium nitrate is 1:1, mixture is heated to 450~600 DEG C in a nitrogen atmosphere, keeps 3~6h；It is natural
Room temperature is cooled to, that is, obtains high-dispersion loading type nano Pt/C o alloy catalysts.
2. the high-dispersion loading type PtCo nanometer alloy catalysts that prepared by a kind of method according to claim 1, wherein receiving
The average grain diameter of rice alloying pellet is 3~10nm, and the weight/mass percentage composition of Pt is for the weight/mass percentage composition of 2.0~5.5%, Co
0.5~2.5%.
3. a kind of application of high-dispersion loading type PtCo nanometer alloy catalysts according to claim 2, the catalyst is used
In the selective hydrogenation of cinnamic acid.
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| CN110013860B (en) * | 2019-04-19 | 2020-07-10 | 西安交通大学 | Preparation method of Pt-cobalt borate catalyst |
| CN111939879B (en) * | 2019-05-17 | 2023-04-07 | 国家纳米科学中心 | Layered dihydroxy compound and porous carbonized melamine composite material as well as preparation method and application thereof |
| CN114849761B (en) * | 2022-06-09 | 2024-04-12 | 东莞理工学院 | Photocatalytic material and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973768A (en) * | 1988-03-08 | 1990-11-27 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| CN101445427A (en) * | 2008-12-30 | 2009-06-03 | 浙江大学 | Method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde |
| CN101716516A (en) * | 2009-11-30 | 2010-06-02 | 赵杰 | Attapulgite loaded cobalt-platinum hydrogenation catalyst and preparation method thereof |
| CN101947448A (en) * | 2010-09-21 | 2011-01-19 | 北京化工大学 | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof |
| CN103601255A (en) * | 2013-10-30 | 2014-02-26 | 中国科学院化学研究所 | Three-dimensional micro/nano hierarchically-structured cobalt-aluminium hydrotalcite material, and preparation method and applications thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973768A (en) * | 1988-03-08 | 1990-11-27 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| CN101445427A (en) * | 2008-12-30 | 2009-06-03 | 浙江大学 | Method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde |
| CN101716516A (en) * | 2009-11-30 | 2010-06-02 | 赵杰 | Attapulgite loaded cobalt-platinum hydrogenation catalyst and preparation method thereof |
| CN101947448A (en) * | 2010-09-21 | 2011-01-19 | 北京化工大学 | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof |
| CN103601255A (en) * | 2013-10-30 | 2014-02-26 | 中国科学院化学研究所 | Three-dimensional micro/nano hierarchically-structured cobalt-aluminium hydrotalcite material, and preparation method and applications thereof |
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