CN109894149A - A kind of composite nanostructure catalyst and its preparation and application - Google Patents
A kind of composite nanostructure catalyst and its preparation and application Download PDFInfo
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Abstract
A kind of composite nanostructure catalyst is made of metal organic framework compound nanoscale twins and the metal nanoparticle two parts being carried on its lamella；The ratio of the amount of the metal organic framework compound nanoscale twins and metal nanoparticle substance is 2:1-50:1.The preparation method of the composite nanostructure catalyst includes the preparation of metal nanometer particle colloid and two steps of preparation of composite nanostructure catalyst.Compared with prior art, catalyst of the present invention have many advantages, such as catalytic activity is excellent, structural constituent can on demand modulation, have wide range of applications；Compared to other preparation methods, the preparation process of this method without high temperature and pressure, reaction condition is mild, controllability is strong, reduces other methods bring uncontrollable factor, practical.
Description
Technical field
The present invention relates to a kind of novel composite nano structure catalyst and preparation method thereof, specifically this composite Nano
There is structure catalyst super thin metal to have a machine frame structure nanoscale twins and metal nanoparticle two parts, lamellar spacing, size,
Nano particle diameter is adjustable, can be used for electrochemical oxygen reduction reaction, oxygen evolution reaction, Hydrogen evolving reaction, small molecular alcohol
In class oxidation reaction, the system of organic molecule electrochemistry formated reaction.
The invention further relates to the preparation methods of above-mentioned composite material.
Background technique
Electrochemical catalysis reaction is in energy technology, analysis and characterization technology, electron and information technology and material synthesis technology
Etc. national economy key areas have irreplaceable role.The structure design and materials synthesis of electrochemical catalyst are the fields
One of core technology.As the continuous development of nanotechnology is in the further investigation of field of energy source materials, there is nanoscale
New material and its special physico-chemical property that has be widely used.Wherein, metal-organic framework (MOFs) is made
For novel nano porous material developed in recent years, since it is with orderly pore structure, high chemical activity, high-specific surface area
Etc. excellent property, there is great application potential in electrochemical catalysis field.Electrochemical catalysis research based on MOFs material,
Having opened at present includes the closely related catalysis reactant of the energy devices such as oxygen reduction reaction (ORR), oxygen evolution reaction (OER)
Relevant catalyst system of material environments such as system and small organic molecule synthesis, carbon dioxide electroreduction etc..But at the same time, I
It has also been found that MOFs material due to its own unstability, electric conductivity is insufficient the defects of, electro-catalysis field application still
It is old to be faced with activity, the severe challenge of stability.
In consideration of it, developing one kind has high activity, high stability, and the novel MOFs catalyst of structure-controllable, it is not
Carry out MOFs material and realize one of committed step of its application value, it is also possible to open up completely new research in electrochemical catalysis field and answer
Use field.
Summary of the invention
The present invention will prepare a kind of novel composite nano structure catalyst, specifically this composite nanostructure catalyst
There are machine frame structure nanoscale twins and metal nanoparticle two parts, lamellar spacing, size, nanoparticle seed with super thin metal
Diameter is adjustable, can be used for electrochemical oxygen reduction reaction, oxygen evolution reaction, Hydrogen evolving reaction, small molecule alcohol oxidation reaction,
In the system of organic molecule electrochemistry formated reaction.
To achieve the above object, the present invention is realized using scheme in detail below:
A kind of composite nanostructure catalyst by metal organic framework compound nanoscale twins and is carried on its lamella
Metal nanoparticle two parts are constituted；The amount of the metal organic framework compound nanoscale twins and metal nanoparticle substance
Than for 2:1-50:1.
The metal organic framework compound is that metal ion and ligand are constituted；The metal ion be nickel, cobalt, copper, iron,
One or more of zirconium；The ligand is one of pyridine and its derivatives, aromatic carboxylic acids and its derivative or two
Kind or more.
The metal nanoparticle is the alloy of one or more of platinum, ruthenium, palladium, gold, silver；The metal nano
The diameter range of particle is 1-20nm.
The metal organic framework compound nanoscale twins with a thickness of 1-10nm.
The preparation method of the composite nanostructure catalyst, preparation and composite Nano including metal nanometer particle colloid
Two steps of preparation of structure catalyst, as shown in Figure 1；
The preparation process of the composite nanostructure catalyst are as follows:
A. transition metal salt is added in the in the mixed solvent of one or more of dimethylformamide, water, ethyl alcohol
Form transition metal salt solution；
B. the organic ligand point of the amount of substance same as transition metal salt is added in the transition metal salt solution described in step a
Son；Metal nanometer particle colloid is then added, ultrasonic disperse is uniform to obtain mixed solution；The metal nanometer particle colloid and transition
The ratio of the amount of substance of metal salt is 1:50 to 1:2；
C. under the conditions of inert gas shielding, 2 to 10 times of substances of metal precursor salts are added in the mixed solution described in step b
The triethylamine of amount, the lower reaction of air-proof condition ultrasonic wave effect, by reaction product washing, separates to obtain composite nanostructure catalyst.
Transition metal salt described in step a is cobalt nitrate, in nickel nitrate, copper nitrate, nitrous acid iron, zirconium chloride, zinc nitrate
One or more, the concentration of transition metal salt solution are 0.1mM-10mM.
Ultrasonic power under the effect of ultrasonic wave described in step c when reaction is 50-500W, and the reaction time is 1-12 hours；
The reaction product washing, separation are specially to be cleaned 4 times or more with ethyl alcohol, and separation is using centrifuge separation, centrifugal rotational speed 2000
To 10000 revs/min, centrifugation time is each 5-10 minutes, and centrifuging temperature is 5-10 DEG C.
The metal nanometer particle colloid is prepared using hydro-thermal method or reduction method.
When the metal nanoparticle is the alloy particle of one of platinum, gold or both with third metal, using hydro-thermal legal system
Standby metal nanometer particle colloid；The third metal is one or more of nickel, cobalt, iron, copper, zirconium；
When the metal nanoparticle is one of gold, palladium, silver, the preparation of colloid is carried out using room temperature reduction method；
The hydro-thermal method is metal precursor to be added in ethylene glycol solvent, and the guarantor that quality is 1-10 times of metal precursor is added
Agent is protected, homogeneous mixture solotion is obtained；It will be heated to 110-150 DEG C under the conditions of gained homogeneous mixture solotion oil bath, react 2-6 hours,
It is cooled to room temperature to obtain metal nanometer particle colloid；The concentration of metal precursor is 1-10mM in the mixed solution；The protection
Agent be one or both of ethylene glycol, polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyacrylic acid (PAA) with
On；
The reduction method is that the amount that metal precursor is added in water or alcohol solvent, and substance is added is metal precursor
2-5 times of reducing agent, reacts 24-72h at room temperature, obtains metal nanometer particle colloid；The metal precursor is dense in solvent
Degree is 1-10mM；The reducing agent be one or both of sodium citrate, sodium oxalate, sodium formate, sodium borohydride, hydrazine hydrate with
On；
The metal precursor be one of chloroplatinic acid, potassium chloroplatinate, ruthenic chloride, chlorine palladium acid, gold chloride, silver nitrate, or
For one of chloroplatinic acid, potassium chloroplatinate, ruthenic chloride, chlorine palladium acid, gold chloride, silver nitrate and nickel nitrate, cobalt nitrate, ferric nitrate,
The mixture of one or more of copper nitrate, zirconium nitrate.
The composite nanostructure catalyst is electrochemical oxygen reduction reaction, oxygen evolution reaction, Hydrogen evolving reaction, small molecule
Any catalyst in oxidation of alcohols reaction, the reaction of organic molecule electrochemistry formated.
Compared with prior art, the invention has the following advantages that
1. catalytic activity is excellent: using the composite nanostructure catalyst of preparation of the present invention in a variety of electrocatalytic reactions
In all have compare traditional catalyst it is more preferably excellent electrochemical catalysis activity；
2. structural constituent can on-demand modulation: the composite nanostructure catalyst prepared using the method for the invention, due to
The controllability of preparation process different step, material component can expand its application range according to reaction requirement just modulation is catalyzed；
3. applied widely: the composite nanostructure catalyst prepared using the method for the invention, suitable for including
A variety of electrocatalytic reaction fields such as oxygen reduction reaction, oxygen evolution reaction, Hydrogen evolving reaction, carbon dioxide electroreduction；
4. practical: compared to other preparation methods, the preparation process of this method is not necessarily to high temperature and pressure, reaction condition temperature
It is strong with controllability, reduce other methods bring uncontrollable factor, it is practical.
Detailed description of the invention
Fig. 1 composite nanostructure catalyst preparation process of the present invention and structural schematic diagram.
The stereoscan photograph (embodiment 1) for the composite nanostructure catalyst that Fig. 2 is prepared using the method for the invention.
As seen from the figure, uniform lamellar structure is showed under microcosmic using catalysis material prepared by the present invention.
Transmission electron microscope photo (2 He of comparative example for the composite nanostructure catalyst that Fig. 3 is prepared using the method for the invention
Embodiment 1).As seen from the figure, metal nanoparticle is uniformly supported in the surface of nanoscale twins.
Fig. 4 (is implemented using the atomic force microscopy of the composite nanostructure catalyst of the method for the invention preparation
Example 1).As seen from the figure, the catalysis material of prepared nano-lamellar structure shows uniform ultra-thin lamellar structure, and thickness is about
2nm。
The electrochemical oxygen reduction test result for the composite nanostructure catalyst that Fig. 5 is prepared using the method for the invention
(embodiment 1-4, comparative example 1).As seen from the figure, the oxygen reduction reaction catalytic activity of embodiment is significantly higher than comparative example.
Fig. 6 tests knot using the electrochemistry oxygen evolution reaction of the composite nanostructure catalyst of the method for the invention preparation
Fruit (embodiment 1-4, comparative example 2).As seen from the figure, the oxygen evolution reaction catalysis activity of embodiment is significantly higher than comparative example.
Specific embodiment
Below by way of example, the present invention is described in detail, but the present invention is not limited only to following embodiment.
Embodiment 1:
A. the preparation of metal nanometer particle colloid
Metal nanometer particle colloid is prepared using hydro-thermal method reduction, the steps include: the chloroplatinic acid for weighing 20mg, is dissolved
In 50mL ethylene glycol solvent, dissolution 30min is sufficiently stirred, oil bath heating reacts 6 hours to 140 DEG C, metal is obtained after cooling
Nano platinum particle colloid.
B. the preparation of composite nanostructure catalyst
200mg nickel nitrate is dissolved in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio 16:1:1, nitric acid
Nickel concentration is 1mM, after completely dissolution, the phthalic acid of the amount of same substance is added, and is sufficiently dissolved；
Metal nano colloid prepared by above-mentioned steps a is then added, additional amount is and transition metal salt the mass ratio of the material
Example is 1:20, persistently stirs 12h at room temperature after ultrasonic disperse is uniform；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time be 5 minutes, centrifuging temperature be 5 DEG C to get arrive the composite nanostructure catalyst.
Comparative example 1:
Comparative example 1 is carbon-supported metal nanoparticle, is prepared using hydro-thermal method reduction, the steps include: to weigh
The chloroplatinic acid of 20mg is dissolved in 50mL ethylene glycol solvent, and dissolution 30min is sufficiently stirred, and for oil bath heating to 140 DEG C, reaction 6 is small
When, 90mg active carbon is added after being cooled to 80 DEG C, obtains carbon-supported metal platinum nano-particle after 4h is sufficiently stirred.
Comparative example 2:
The super thin metal organic framework material that comparative example 2 supports for no metal nanoparticle.200mg nickel nitrate is molten
Solution is 1mM in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio 16:1:1, nitric acid nickel concentration, after completely dissolution,
The phthalic acid of the amount of same substance is added, sufficiently dissolves；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time is 5 minutes, and centrifuging temperature is 5 DEG C to get the catalyst for arriving comparative example 2.
Embodiment 2:
A. the preparation of metal nanometer particle colloid
Metal nanometer particle colloid is prepared using hydro-thermal method reduction, the steps include: the chloroplatinic acid for weighing 20mg, is dissolved
In 50mL ethylene glycol solvent, dissolution 30min is sufficiently stirred, oil bath heating reacts 6 hours to 140 DEG C, metal is obtained after cooling
Nano platinum particle colloid.
B. the preparation of composite nanostructure catalyst
200mg cobalt nitrate is dissolved in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio 16:1:1, nitric acid
Nickel concentration is 1mM, after completely dissolution, the trimesic acid of the amount of same substance is added, and is sufficiently dissolved；
Metal nano colloid prepared by above-mentioned steps a is then added, additional amount is and transition metal salt the mass ratio of the material
Example is 1:20, persistently stirs 12h at room temperature after ultrasonic disperse is uniform；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time be 5 minutes, centrifuging temperature be 5 DEG C to get arrive the composite nanostructure catalyst.
Embodiment 3:
A. the preparation of metal nanometer particle colloid
Metal nanometer particle colloid is prepared using hydro-thermal method reduction, the steps include: the chloroplatinic acid for weighing 20mg, is dissolved
In 50mL ethylene glycol solvent, dissolution 30min is sufficiently stirred, oil bath heating reacts 6 hours to 140 DEG C, metal is obtained after cooling
Nano platinum particle colloid.
B. the preparation of composite nanostructure catalyst
200mg copper nitrate is dissolved in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio 16:1:1, nitric acid
Nickel concentration is 1mM, after completely dissolution, the pyridine of the amount of same substance is added, and is sufficiently dissolved；
Metal nano colloid prepared by above-mentioned steps a is then added, additional amount is and transition metal salt the mass ratio of the material
Example is 1:20, persistently stirs 12h at room temperature after ultrasonic disperse is uniform；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time be 5 minutes, centrifuging temperature be 5 DEG C to get arrive the composite nanostructure catalyst.
Embodiment 4:
A. the preparation of metal nanometer particle colloid
Metal nanometer particle colloid is prepared using hydro-thermal method reduction, the steps include: the chloroplatinic acid for weighing 20mg, is dissolved
In 50mL ethylene glycol solvent, dissolution 30min is sufficiently stirred, oil bath heating reacts 6 hours to 140 DEG C, metal is obtained after cooling
Nano platinum particle colloid.
B. the preparation of composite nanostructure catalyst
200mg ferrous nitrate is dissolved in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio 16:1:1, nitre
Sour nickel concentration is that the 2-2 bipyridyl of the amount of same substance is added after completely dissolution in 1mM, is sufficiently dissolved；
Metal nano colloid prepared by above-mentioned steps a is then added, additional amount is and transition metal salt the mass ratio of the material
Example is 1:20, persistently stirs 12h at room temperature after ultrasonic disperse is uniform；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time be 5 minutes, centrifuging temperature be 5 DEG C to get arrive the composite nanostructure catalyst.
Embodiment 5:
A. the preparation of metal nanometer particle colloid
Metal nanometer particle colloid is prepared using room temperature reduction method, the steps include: to weigh the chloroplatinic acid of 20mg with
20mg ruthenic chloride is dissolved in 40mL aqueous solution, and dissolution 30min is sufficiently stirred, the formic acid of the amount of 4 times of substances of metal salt is added
Potassium after being placed at room temperature for for 24 hours, obtains metal platinum nano-particle colloid.
B. the preparation of composite nanostructure catalyst
100mg nickel nitrate and 100mg cobalt nitrate are dissolved in the in the mixed solvent of dimethylformamide, water, ethyl alcohol, ratio
For 8:1:1, metal salt concentrations 1mM, after completely dissolution, the phthalic acid and 0.5 times of substance of the amount of 0.5 times of substance is added
The pyridine of amount sufficiently dissolves；
Metal nano colloid prepared by above-mentioned steps a is then added, additional amount is and transition metal salt the mass ratio of the material
Example is 1:20, persistently stirs 12h at room temperature after ultrasonic disperse is uniform；
The triethylamine of the amount of 4 times of substances of metal precursor salts, air-proof condition are then rapidly joined under conditions of nitrogen protection
Ultrasonic wave effect is lower to react 6h, ultrasonic power 200W；
It is cleaned 4 times using the method for centrifuge separation with ethyl alcohol after reaction, centrifugal rotational speed is 5000 rpms, every time
Centrifugation time be 5 minutes, centrifuging temperature be 5 DEG C to get arrive the composite nanostructure catalyst.
Claims (10)
1. a kind of composite nanostructure catalyst, it is characterised in that: by metal organic framework compound nanoscale twins and be carried on
Metal nanoparticle two parts on its lamella are constituted；The metal organic framework compound nanoscale twins and metal nanoparticle
The ratio of the amount of substance is 2:1-50:1.
2. composite nanostructure catalyst as described in claim 1, it is characterised in that: the metal organic framework compound is gold
Belong to ion and ligand is constituted；The metal ion is one or more of nickel, cobalt, copper, iron, zirconium；The ligand is pyrrole
One or more of pyridine and its derivative, aromatic carboxylic acids and its derivative.
3. composite nanostructure catalyst as described in claim 1, it is characterised in that: the metal nanoparticle be platinum, ruthenium,
The alloy of one or more of palladium, gold, silver；The diameter range of the metal nanoparticle is 1-20nm.
4. composite nanostructure catalyst as described in claim 1, it is characterised in that: the metal organic framework compound nanometer
Lamella with a thickness of 1-10nm.
5. a kind of preparation method of any composite nanostructure catalyst of claim 1-4, it is characterised in that: including metal
The preparation of nanometer particle colloid and two steps of preparation of composite nanostructure catalyst；
The preparation process of the composite nanostructure catalyst are as follows:
A. it is formed in the in the mixed solvent addition transition metal salt of one or more of dimethylformamide, water, ethyl alcohol
Transition metal salt solution；
B. the organic ligand molecule of the amount of substance same as transition metal salt is added in the transition metal salt solution described in step a；
Metal nanometer particle colloid is then added, ultrasonic disperse is uniform to obtain mixed solution；The metal nanometer particle colloid and transition gold
The ratio for belonging to the amount of substance of salt is 1:50 to 1:2；
C. under the conditions of inert gas shielding, 2 to 10 times of amount of substance of metal precursor salts are added in the mixed solution described in step b
Triethylamine, the lower reaction of air-proof condition ultrasonic wave effect, by reaction product washing, separates to obtain composite nanostructure catalyst.
6. the preparation method of composite nanostructure catalyst as claimed in claim 5, it is characterised in that: mixing described in step a is molten
Dimethylformamide in agent, water, ethyl alcohol volume ratio be 8:1:1 to 32:1:1, transition metal salt is cobalt nitrate, nickel nitrate, nitre
One or more of sour copper, nitrous acid iron, zirconium chloride, zinc nitrate, the concentration of transition metal salt solution are 0.1mM-
10mM。
7. the preparation method of composite nanostructure catalyst as claimed in claim 5, it is characterised in that: ultrasonic wave described in step c
Ultrasonic power under effect when reaction is 50-500W, and the reaction time is 1-12 hours；The reaction product washing, separation tool
Body is to be cleaned 4 times or more with ethyl alcohol, and separation is using centrifuge separation, and centrifugal rotational speed is 2000 to 10000 revs/min, centrifugation time
To be 5-10 minutes each, centrifuging temperature is 5-10 DEG C.
8. the preparation method of composite nanostructure catalyst as claimed in claim 5, it is characterised in that: the metal nanoparticle
Colloid is prepared using hydro-thermal method or reduction method.
9. the preparation method of composite nanostructure catalyst as claimed in claim 8, it is characterised in that:
When the metal nanoparticle is the alloy particle of one of platinum, gold or both with third metal, gold is prepared using hydro-thermal method
Belong to nanometer particle colloid；The third metal is one or more of nickel, cobalt, iron, copper, zirconium；
When the metal nanoparticle is one of gold, palladium, silver, the preparation of colloid is carried out using room temperature reduction method；
The hydro-thermal method is metal precursor to be added in ethylene glycol solvent, and the protective agent that quality is 1-10 times of metal precursor is added,
Obtain homogeneous mixture solotion；It will be heated to 110-150 DEG C under the conditions of gained homogeneous mixture solotion oil bath, react 2-6 hours, be down to room
Metal nanometer particle colloid is obtained after temperature；The concentration of metal precursor is 1-10mM in the mixed solution；The protective agent is second
One or more of glycol, polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyacrylic acid (PAA)；
The reduction method is that the amount that metal precursor is added in water or alcohol solvent, and substance is added is 2-5 times of metal precursor
Reducing agent, react 24-72h at room temperature, obtain metal nanometer particle colloid；Concentration of the metal precursor in solvent is 1-
10mM；The reducing agent is one or more of sodium citrate, sodium oxalate, sodium formate, sodium borohydride, hydrazine hydrate；
The metal precursor is one of chloroplatinic acid, potassium chloroplatinate, ruthenic chloride, chlorine palladium acid, gold chloride, silver nitrate, or is chlorine
One of platinic acid, potassium chloroplatinate, ruthenic chloride, chlorine palladium acid, gold chloride, silver nitrate and nickel nitrate, cobalt nitrate, ferric nitrate, nitric acid
The mixture of one or more of copper, zirconium nitrate.
10. a kind of application of any composite nanostructure catalyst of claim 1-4, it is characterised in that: described compound to receive
Rice structure catalyst is electrochemical oxygen reduction reaction, oxygen evolution reaction, Hydrogen evolving reaction, small molecule alcohol oxidation reaction, organic
Any catalyst in the reaction of molecule electrochemistry formated.
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| CN111450891B (en) * | 2020-04-09 | 2021-09-03 | 中国科学院化学研究所 | Deformable metal organic framework nanosheet catalyst and preparation method and application thereof |
| CN112657557A (en) * | 2021-01-06 | 2021-04-16 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol |
| CN112657557B (en) * | 2021-01-06 | 2023-04-07 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of phenol |
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