CN107308976A - A kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application - Google Patents
A kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application Download PDFInfo
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- CN107308976A CN107308976A CN201710553830.0A CN201710553830A CN107308976A CN 107308976 A CN107308976 A CN 107308976A CN 201710553830 A CN201710553830 A CN 201710553830A CN 107308976 A CN107308976 A CN 107308976A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Abstract
The invention discloses a kind of N doping Carbon Materials load palladium-based catalyst and preparation method and application.The present invention is by the way that N doping Carbon Materials are added in alcoholic solution, after ultrasonic 5min ~ 30min, adds 1wt% ~ 4.2wt% palladium precursor solution, obtains raw catalyst；Raw catalyst is heated to reflux the h of stirring 4 ~ 12 again, 10ml ~ 20ml 1M/L NaBH is added4, continue to stir the h of 1h ~ 2, filtering, washing, vacuum drying obtain N doping Carbon Materials load palladium-based catalyst.Catalyst nitrogen of the present invention is using N doping Carbon Materials as catalyst carrier, and precious metal palladium is carried on carrier with a scattered manner, and the load capacity of palladium is the wt% of 1.0 wt% ~ 5.0 in catalyst.In terms of catalyst of the present invention is applied to catalysis formates preparation.Catalyst of the present invention is simple to manufacture, materials are cheap, and catalyst activity is strong, reusable, simple to operate.
Description
Technical field
The invention belongs to compound catalysts field, more particularly to a kind of N doping Carbon Materials load palladium-based catalyst
And preparation method and application.
Background technology
Porous carbon material have flourishing hole, high specific surface area, good chemical stability, acid and alkali-resistance, high temperature resistant,
Conductive, heat conduction and a series of low features of cost, are one of indispensable important materials in modern industry, are widely used in electricity
Pole material（Such as fuel cell, ultracapacitor）, sorbing material, the field such as energy storage material and catalyst carrier.
N doping Carbon Materials obtain express delivery development in recent years, are primarily due to introduce after nitrogen-atoms on carbon skeleton, to raw material of wood-charcoal
The property influence of material is very big.The nitrogen-atoms of high electron density has a significant impact to the band structure of Carbon Materials, due to covalent band
Reduction, material is more stable in chemistry, improves the electron density on fermi level.Meanwhile, for raw material of wood-charcoal after doping nitrogen-atoms
The surface alkalinty of material has very big change, and the nitrogen of structure doping is conducive to the raising of the lewis base property of material.This causes N doping
Carbon Materials have good application potential in terms of catalysis.The chemical environment of the nitrogen-atoms of doping be influence Carbon Materials it is important because
Element, pyridine type nitrogen has lone pair electrons, if this pyridine nitrogen functional group is introduced in Carbon Materials is greatly improved leading for Carbon Materials
Electrical and basic site, so as to increase its interaction with metal, increases the stability of catalyst.
Being presently used for the method for nitrogenous porous carbon materials synthesis has a lot, is broadly divided into doping method in situ and post treatment method.
In-situ synthesis is typically that nitrogen source is introduced in Carbon Materials building-up process or carbon source containing nitrogen itself is used, in carbon forerunner
In the carbonisation of body, inside nitrogen-atoms incorporation Carbon Materials, nitrogen is evenly distributed in resulting N doping porous charcoal, and
Mainly exist in the form of structure nitrogen.Post processing is to carry out surface chemical modification processing to the Carbon Materials prepared, such as
High-temperature heat treatment or liquid impregnation nitrogen source Low Temperature Heat Treatment, mainly exist with modification type nitrogen form.Doping method in situ and post processing
The problem of there are expensive starting materials, prepare complicated in method.
Prepared based on the masterplate method reported in N doping Carbon Materials method, stress constructing for material pore passage structure
（Vinu, A.; Ariga, K.; Mori, T.; Nakanishi, T.; Hishita, S.; Golberg, D.;
Bando, Y. Preparation and Characterization of Well-Ordered Hexagonal
Mesoporous Carbon Nitride. Adv. Mater. 2005, 17, 1648-1652）, and for the nitrogen thing of doping
Plant and lack research, will especially prepare N doping Carbon Materials supported catalyst is used in terms of hydrogenation of carbon dioxide formic acid be even more one
Individual blank.
The content of the invention
Palladium-based catalyst is loaded it is an object of the invention to provide a kind of N doping Carbon Materials based on pyridine nitrogen.
Urged it is still another object of the present invention to provide a kind of cheap, the simple to operate N doping Carbon Materials load palladium base of raw material
The preparation method of agent.
The concrete application of palladium-based catalyst is loaded another object of the present invention is to provide above-mentioned N doping Carbon Materials.
The present invention is achieved in that a kind of N doping Carbon Materials load palladium-based catalyst, and the catalyst nitrogen is with N doping
Carbon Materials are catalyst carrier；Precious metal palladium is carried on carrier in high dispersive mode, and in the catalyst palladium load capacity
For the wt% of 1.0 wt% ~ 5.0.
The present invention further discloses the preparation method that above-mentioned N doping Carbon Materials load palladium-based catalyst, this method is used
Different polyethylene polyamines is that with carbon tetrachloride polymerisation, the raw material of wood-charcoal of the new N doping prepared through high-temperature process occur for nitrogen source
Material is that carrier loaded Pd nano particle is catalyst, and more specifically, this method comprises the following steps：
（1）N doping Carbon Materials are added in alcoholic solution, after ultrasonic 5min ~ 30min, 1wt% ~ 4.2wt% palladium forerunner are added
Liquid solution, obtains raw catalyst；The quality volume of the N doping Carbon Materials, alcoholic solution, palladium contained by palladium precursor solution
Than for 0.5g：100ml：（10~30）mg；Wherein, palladium content contained by palladium precursor solution（Or palladium precursor solution volume is really
The fixed palladium load capacity in catalyst is determined）；
（2）By step（1）Middle raw catalyst is heated to reflux the h of stirring 4 ~ 12, adds 10ml ~ 20ml 1M/L NaBH4,
Continue to stir the h of 1h ~ 2, filtering, washing, vacuum drying obtain the N doping Carbon Materials load palladium-based catalyst of high dispersive（This is urged
Agent be represented by the chemical formula for：Pd/NC-x-y）；The mol ratio of palladium and sodium borohydride is 1 in the raw catalyst：（20~
60）.
Preferably, in step（1）In, the alcohol is at least one of methanol, ethanol, normal propyl alcohol and isopropanol；It is described
Palladium precursor solution is the hydrochloric acid solution for being dissolved with palladium bichloride；
Preferably, in step（1）In, the preparation of the N doping Carbon Materials comprises the following steps：
A, ethylene polyamine and carbon tetrachloride be added in SBA15, be heated to 90oC ~ 120 DEG C to the 4h ~ 6h that flows back, gained is consolidated
Body, which is placed in baking oven under 100oC, dries 12h, is calcined after dried object grinding in nitrogen atmosphere；The ethylene polyamine, carbon tetrachloride
Mol ratio be（0.5~1）：1；The mass ratio of the SBA15 and carbon tetrachloride（0.1~0.2）：1；
B, calcining products therefrom pickling removed into hard template, N doping Carbon Materials are obtained after water and ethanol washing, vacuum drying（Should
Material is represented by the chemical formula as NC-x-y, wherein, x represents presoma, and y represents calcining heat）.
Preferably, in step, the polyethylene polyamine is diethylenetriamine, triethylene tetramine, TEPA and gathered
At least one of aziridine；
In step, the concrete operations of the calcining are：400 ~ 800 DEG C are warming up in tube furnace with 2.5 ~ 5.0 DEG C/min to forge
Burn 2h ~ 5h.
Preferably, the molecular weight of the polyethyleneimine is 600,1800.
Preferably, in stepb, the pickling concrete operations are：Calcining products therefrom is cooled to after room temperature and uses 8 wt
% hydrofluoric acid or 8 wt % ammonium fluoride cleaning remove template.
Preferably, in step（2）In, the heating-up temperature being heated to reflux is 60 ~ 100oC。
Palladium-based catalyst is loaded in terms of catalysis prepares formates the present invention further discloses above-mentioned N doping Carbon Materials
Application.
Preferably, the method for the application comprises the following steps：N doping Carbon Materials are loaded into palladium-based catalyst, water, alkali, two
Carbonoxide, hydrogen are added in autoclave, and corresponding first Acid-Base compound, i.e. formates are obtained after reaction；Wherein,
The consumption of N doping Carbon Materials load palladium-based catalyst by addition alkali weight the % of 0.1 % ~ 20；The alkali exists
Mass concentration in water is the mol/L of 1mol/L ~ 4；
The temperature of the reaction is 80 DEG C ~ 160 DEG C, and the time is 12h ~ 48h, and pressure is the MPa of 2MPa ~ 8；, the reaction temperature is easy
Control, running cost is low；In addition, it is different according to the species of alkali, the reaction time can be suitably adjusted, until pressure is constant；
The hydrogen and CO2Pressure ratio is（1~3）：1.
Catalyst of the present invention is added in autoclave with water, carbon dioxide, alkali, hydrogen, obtains corresponding after reaction
First Acid-Base compound, in the reaction system, catalyst and the amount influence reaction rate and conversion ratio for adding alkali；The addition of alkali
It is in order to which the formic acid of generation is quickly converted into formates, so that reaction proceeds.
Preferably, the alkali is sodium hydroxide, potassium hydroxide, triethylamine, sodium acid carbonate, saleratus and ammonium hydrogen carbonate
It is at least one.
The present invention overcomes the deficiencies in the prior art, and there is provided a kind of N doping Carbon Materials load palladium-based catalyst and its preparation side
Method and application.The different nitrogenous precursor of present invention selection, polymerize, Ran Houtong with carbon tetrachloride in SBA15 duct first
The species of the nitrogen species in pyrolysis temperature control material is overregulated, occurs strong phase interaction with palladium using the nitrogen species adulterated in material
With, while Pd nano particle is stablized to its electronic state carry out accuracy controlling, and utilize its high nitrogen-containing CO absorption2Play richness
Collect the purpose of reaction substrate concentration, activate CO jointly2Formic acid processed.
Compared to the shortcoming and defect of prior art, the invention has the advantages that：
（1）The present invention uses different polyethylene polyamines to be that polymerisation occurs for nitrogen source and carbon tetrachloride, is prepared through high-temperature process
New N doping Carbon Materials be that carrier loaded Pd nano particle is catalyst, can realize CO in the presence of base2Reduction
For formic acid（Salt）, it is practical, and reaction condition is gentle, it is easy to operate；
（2）The present invention is that nitrogen source, carbon tetrachloride are carbon source from different polyethylene polyamines, prepares the high-area carbon of new N doping,
It is used for catalytic activation CO by controlling calcining heat accuracy controlling nitrogen content and nitrogen species, and by its supported palladium2Formates processed, choosing
Selecting property is 100%, and reaction condition is gentle；
（3）Catalyst of the present invention only need to can obtain reacting liquid filtering corresponding formic acid-aqueous slkali after catalytic reaction terminates,
Catalyst is washed with ethanol, drying be it is reusable, it is simple to operate, and activity do not reduce.
Brief description of the drawings
Fig. 1 is the BET figures of N doping Carbon Materials in the embodiment of the present invention 1；
Fig. 2 is the pore size distribution figure of N doping Carbon Materials in the embodiment of the present invention 1；
Fig. 3 is N doping Carbon Materials SEM figures in the embodiment of the present invention 1；
Fig. 4 is the TEM figures of N doping Carbon Materials in the embodiment of the present invention 1；
Fig. 5 is the full spectrograms of XPS of N doping Carbon Materials in the embodiment of the present invention 1；
Fig. 6 is the XPS swarming fitted figures of N doping Carbon Materials N1s in the embodiment of the present invention 1；
The HR-TEM figures of N doping Carbon Materials load palladium-based catalyst in Fig. 7 embodiment of the present invention 1.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
By diethylenetriamine（a）In 3.35g, carbon tetrachloride 5.0g, the round-bottomed flask for being added to the SBA15 containing 0.5g, heating
Flowed back 4h to 90oC, obtain brown solid, be put into baking oven 100oC and dry 12h, be put into tube furnace in nitrogen atmosphere with
2.5oC/min is warming up to 400oC polymerization 4h, is cooled to after room temperature and removes template with 8 wt % hydrofluoric acid, after washing is dried, obtains
The N doping Carbon Materials NC-a-400 of black.
Each correlation performance parameters analysis is carried out to N doping Carbon Materials NC-a-400, as shown in Fig. 1 ~ 7.This pair of N doping charcoal
Material NC-a-400 specific surface areas are 296m2/ g, pore volume is 0.35cm3/ g, aperture is 4.6nm；SEM figures are shown, from N1s's
XPS swarming fitted figures can be seen that mainly two kinds of N, be the nitrogen of the pyridine type at 398.3 eV, 400.4 eV respectively
Locate the nitrogen of pyrroles's type.
In 250 ml round-bottomed flasks, the addition new N doping Carbon Materials NC-a-400 of 0.5 g, 100 ml absolute methanols,
Ultrasonic vibration 20min, adds the PdCl containing 10 mg palladiums2Solution, the min of ultrasonic vibration 20 is heated to reflux stirring 12 h, plus
Enter the M/L NaBH of 10 ml 14, continue to stir 1 h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials
The palladium catalyst Pd/NC-a-400 of load, can be seen that Metal Palladium average particle size is 2.3nm, Metal Palladium from TEM electron microscopes
Mass fraction in the catalyst is 1.5wt %.
20.0 mg Pd/NC-a-400 catalyst are loaded into 30ml autoclaves, the M/L tri- of 10.0 ml 1.0 are added
Ethylamine solution, it is closed, after nitrogen displacement three times, 3.0 MPa CO are filled with successively2, 3.0 MPa H2, 24 h are reacted under 120oC,
Room temperature is cooled to, carefully residual gas is released, catalyst is centrifuged, the concentration liquid-phase chromatographic analysis of formates is 0.52
M/L, selectivity is 100%.
Embodiment 2
By triethylene tetramine 4.77g（b）, carbon tetrachloride 5.0g, in the round-bottomed flask for being added to the SBA15 containing 0.5g, heating
To 100oC backflow 4h, dark brown solid is obtained, 100oC in baking oven is put into and dries 12h, be put into tube furnace in nitrogen atmosphere
500oC polymerization 4h are warming up to 3.0oC/min, is cooled to after room temperature and removes template with 8 wt % hydrofluoric acid, after washing is dried,
Obtain the N doping Carbon Materials NC-b-500 of black.
In 250 ml round-bottomed flasks, the addition new N doping Carbon Materials NC-b-500 of 0.5 g, 100 ml absolute ethyl alcohols,
Ultrasonic vibration 20min, adds the PdCl containing 20 mg palladiums2Solution, the min of ultrasonic vibration 20 is heated to reflux stirring 12 h, plus
Enter the M/L NaBH of 15 ml 14, continue to stir 1h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials and born
The palladium catalyst Pd/NC-b-500 of load, the average grain diameter of Metal Palladium particle is 2.5nm, Metal Palladium quality in the catalyst point
Number is 3.5wt %.
20.0 mg Pd/NC-b-500 catalyst are loaded into 30ml autoclaves, the M/L hydrogen of 10.0 ml 1.0 is added
Potassium oxide solution, it is closed, after nitrogen displacement three times, 2.0 MPa CO are filled with successively2, 2.0 MPa H2, 12 are reacted under 100oC
H, is cooled to room temperature, carefully releases residual gas, and catalyst is centrifuged, and the concentration of formates is with liquid-phase chromatographic analysis
0.58 M/L, selectivity is 100%.
Embodiment 3
By TEPA（c）In 6.2g, carbon tetrachloride 5.0g, the round-bottomed flask for being added to the SBA15 containing 0.5g, it is warming up to
110oC flows back 5h, obtains dark brown solid, is put into baking oven 100oC and dries 12h, be put into tube furnace in nitrogen atmosphere with
4.0oC/min is warming up to 600oC polymerization 5h, is cooled to after room temperature and removes template with 8 wt % ammonium fluoride, after washing is dried, obtains
The new N doping Carbon Materials NC-c-600 of black.
In 250 ml round-bottomed flasks, the new N doping Carbon Materials NC-c-600 of 0.5 g, 100 ml propyl alcohol, ultrasound are added
20min is shaken, the PdCl containing 30 mg palladiums is added2Solution, the min of ultrasonic vibration 20 is heated to reflux stirring 12 h, adds 20
ml 1 M/L NaBH4, continue to stir 1 h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials load
Palladium catalyst Pd/NC-c-600, the average grain diameter of Metal Palladium particle is 2.8nm, and the mass fraction of Metal Palladium in the catalyst is
5.0wt %。
20.0 mg Pd/NC-c-600 catalyst are loaded into 30ml autoclaves, the M/L hydrogen of 10.0 ml 1.0 is added
Sodium hydroxide solution, it is closed, after nitrogen displacement three times, 2.0 MPa CO are filled with successively2, 2.0 MPa H2, 16 are reacted under 80oC
H, is cooled to room temperature, carefully releases residual gas, and catalyst is centrifuged, and the concentration of formates is with liquid-phase chromatographic analysis
0.63 M/L, selectivity is 100%.
Embodiment 4
By polyethyleneimine（Mean molecule quantity 600）（d）9.8g, carbon tetrachloride 5.0g, are added to the circle of the SBA15 containing 0.5g
In the flask of bottom, 120oC backflow 6h are warming up to, dark brown solid is obtained, be put into 100oC in baking oven and dry 12h, in tubular type after drying
Nitrogen atmosphere is warming up to 700oC polymerization 2h with 5.0oC/min in stove, is cooled to after room temperature and removes mould from 8 wt % ammonium fluoride
Plate, after washing is dried, obtains the new N doping Carbon Materials NC-d-700 of black.
In 250 ml round-bottomed flasks, the addition new N doping Carbon Materials NC-d-700 of 0.5 g, 100 ml absolute methanols,
Ultrasonic vibration 30min, adds the PdCl containing 25 mg palladiums2Solution, the min of ultrasonic vibration 20 is heated to reflux stirring 12 h, plus
Enter the M/L NaBH of 20 ml 14, continue to stir 1 h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials
The monatomic palladium catalyst Pd/NC-d-700 of load, the average grain diameter of Metal Palladium particle is 2.6nm, and Metal Palladium is in the catalyst
Mass fraction be 4.5wt %.
20.0 mg Pd/NC-d-700 catalyst are loaded into 30ml autoclaves, the M/L carbon of 10.0 ml 1.0 is added
Potassium hydrogen phthalate solution, it is closed, after nitrogen displacement three times, 4.0 MPa CO are filled with successively2, 4.0 MPa H2, 12 are reacted under 80oC
H, is cooled to room temperature, carefully releases residual gas, and catalyst is centrifuged, and the concentration of formates is with liquid-phase chromatographic analysis
0.78 M/L, selectivity is 100%.
Embodiment 5
By polyethyleneimine（Mean molecule quantity 1800）（d）9.8g, carbon tetrachloride 5.0g, are added to the SBA15's containing 0.5g
In round-bottomed flask, 120oC backflow 6h are warming up to, dark brown solid is obtained, be put into 100oC in baking oven and dry 12h, in pipe after drying
Nitrogen atmosphere is warming up to 800oC polymerization 2h with 5.0oC/min in formula stove, is cooled to after room temperature and removes mould from 8 wt % ammonium fluoride
Plate, after washing is dried, obtains the new N doping Carbon Materials NC-d-800 of black.
In 250 ml round-bottomed flasks, the addition new N doping Carbon Materials NC-d-800 of 0.5 g, 100 ml absolute methanols,
Ultrasonic vibration 30min, adds the PdCl containing 20 mg palladiums2Solution, the min of ultrasonic vibration 30 is heated to reflux stirring 12 h, plus
Enter the M/L NaBH of 20 ml 14, continue to stir 1 h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials
The monatomic palladium catalyst Pd/NC-d-800 of load, the average grain diameter of Metal Palladium particle is 3.5nm, and Metal Palladium is in the catalyst
Mass fraction be 4.0wt %.
20.0 mg Pd/NC-d-800 catalyst are loaded into 30ml autoclaves, the M/L carbon of 10.0 ml 1.0 is added
Sour hydrogen sodium solution, it is closed, after nitrogen displacement three times, 3.0 MPa CO are filled with successively2, 3.0 MPa H2, 12 are reacted under 100oC
H, is cooled to room temperature, carefully releases residual gas, and catalyst is centrifuged, and the concentration of formates is with liquid-phase chromatographic analysis
0.65 M/L, selectivity is 100%.
Embodiment 6
By polyethylene polyamine（The co-product of diethylenetriamine, triethylene tetramine and TEPA, mean molecule quantity 275）（e）
In 4.5g, carbon tetrachloride 5.0g, the round-bottomed flask for being added to the SBA15 containing 0.5g, 95oC backflow 4h are warming up to, obtain reddish brown
Color solid, is put into 100oC in baking oven and dries 12h, nitrogen atmosphere is warming up to 550oC with 2.5oC/min in tube furnace after drying
It polymerize 4h, is cooled to after room temperature and removes template with 8 wt % hydrofluoric acid, after washing is dried, obtain the new N doping raw material of wood-charcoal of black
Expect NC-e-550.
In 250 ml round-bottomed flasks, the addition new N doping Carbon Materials NC-e-550 of 0.5 g, 100 ml absolute methanols,
Ultrasonic vibration 30min, adds the PdCl containing 15 mg palladiums2Solution, the min of ultrasonic vibration 30 is heated to reflux stirring 12 h, plus
Enter the M/L NaBH of 20 ml 14, continue to stir 2 h, cool down, filter, wash, vacuum drying produces new N doping Carbon Materials
The monatomic palladium catalyst Pd/NC-e-550 of load, the average grain diameter of Metal Palladium particle is 1.9nm, and Metal Palladium is in the catalyst
Mass fraction be 2.5wt %.
20.0 mg Pd/NC-e-550 catalyst are loaded into 30ml autoclaves, the M/L tri- of 10.0 ml 1.0 are added
Ethylamine solution, it is closed, after nitrogen displacement three times, 4.0 MPa CO are filled with successively2, 4.0 MPa H2, 24 h are reacted under 140oC,
Room temperature is cooled to, carefully residual gas is released, catalyst is centrifuged, the concentration liquid-phase chromatographic analysis of formates is 0.78
M/L, selectivity is 100%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of N doping Carbon Materials load palladium-based catalyst, it is characterised in that the catalyst nitrogen is using N doping Carbon Materials to urge
Agent carrier；Precious metal palladium is carried on carrier with a scattered manner, and the load capacity of palladium is 1.0 wt% ~ 5.0 in the catalyst
wt%。
2. the N doping Carbon Materials described in claim 1 load the preparation method of palladium-based catalyst, it is characterised in that this method bag
Include following steps：
（1）N doping Carbon Materials are added in alcoholic solution, after ultrasonic 5min ~ 30min, 1wt% ~ 4.2wt% palladium forerunner are added
Liquid solution, obtains raw catalyst；The quality volume of the N doping Carbon Materials, alcoholic solution, palladium contained by palladium precursor solution
Than for 0.5g：100ml：（10~30）mg；
（2）By step（1）Middle raw catalyst is heated to reflux the h of stirring 4 ~ 12, adds 10ml ~ 20ml 1M/L NaBH4, after
The h of continuous stirring 1h ~ 2, filtering, washing, vacuum drying obtain the N doping Carbon Materials load palladium-based catalyst of high dispersive；It is described not
The mol ratio of palladium and sodium borohydride is 1 in reducing catalyst：（20~60）.
3. N doping Carbon Materials as claimed in claim 2 load the preparation method of palladium-based catalyst, it is characterised in that in step
（1）In, the alcohol is at least one of methanol, ethanol, normal propyl alcohol and isopropanol；The palladium precursor solution is to be dissolved with chlorine
Change the hydrochloric acid solution of palladium；
In step（1）In, the preparation of the N doping Carbon Materials comprises the following steps：
A, ethylene polyamine and carbon tetrachloride be added in SBA15, be heated to 90oC ~ 120 DEG C to the 4h ~ 6h that flows back, gained is consolidated
Body, which is placed in baking oven under 100oC, dries 12h, is calcined after dried object grinding in nitrogen atmosphere；The ethylene polyamine, carbon tetrachloride
Mol ratio be（0.5~1）：1；The mass ratio of the SBA15 and carbon tetrachloride（0.1~0.2）：1；
B, calcining products therefrom pickling removed into hard template, N doping Carbon Materials are obtained after water and ethanol washing, vacuum drying.
4. N doping Carbon Materials as claimed in claim 3 load the preparation method of palladium-based catalyst, it is characterised in that in step
In A, the polyethylene polyamine is at least one of diethylenetriamine, triethylene tetramine, TEPA and polyethyleneimine；
In step, the concrete operations of the calcining are：400 ~ 800 DEG C are warming up in tube furnace with 2.5 ~ 5.0 DEG C/min to forge
Burn 2h ~ 5h.
5. N doping Carbon Materials as claimed in claim 4 load the preparation method of palladium-based catalyst, it is characterised in that described poly-
The molecular weight of aziridine is 600,1800.
6. N doping Carbon Materials as claimed in claim 3 load the preparation method of palladium-based catalyst, it is characterised in that in step
In B, the pickling concrete operations are：Calcining products therefrom is cooled to hydrofluoric acid or 8 wt % fluorine after room temperature with 8 wt %
Change ammonium cleaning and remove template.
7. N doping Carbon Materials as claimed in claim 2 load the preparation method of palladium-based catalyst, it is characterised in that in step
（2）In, the heating-up temperature being heated to reflux is 60 ~ 100oC。
8. application of the N doping Carbon Materials load palladium-based catalyst in terms of catalysis prepares formates described in claim 1.
9. application as claimed in claim 8, it is characterised in that the method for the application comprises the following steps：By N doping raw material of wood-charcoal
Material load palladium-based catalyst, water, alkali, carbon dioxide, hydrogen are added in autoclave, obtained after reaction corresponding formic acid-
Alkali compound, i.e. formates；Wherein,
The consumption of N doping Carbon Materials load palladium-based catalyst by addition alkali weight the % of 0.1 % ~ 20；The alkali exists
Mass concentration in water is the mol/L of 1mol/L ~ 4；
The temperature of the reaction is 80 DEG C ~ 160 DEG C, and the time is 12h ~ 48h, and pressure is the MPa of 2MPa ~ 8；
The hydrogen and CO2Pressure ratio is（1~3）：1.
10. application as claimed in claim 9, it is characterised in that the alkali is sodium hydroxide, potassium hydroxide, triethylamine, carbonic acid
At least one of hydrogen sodium, saleratus and ammonium hydrogen carbonate.
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| CN108554432A (en) * | 2018-04-09 | 2018-09-21 | 陕西理工大学 | A kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and preparation method and application |
| CN109833914A (en) * | 2019-03-20 | 2019-06-04 | 河北工业大学 | A kind of palladium catalyst and its preparation method and application of Cu Base Metal organic frame load |
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| CN114210327A (en) * | 2021-12-28 | 2022-03-22 | 润泰化学（泰兴）有限公司 | Preparation method of catalyst for preparing isobutyl isobutyrate by adopting Tishchenko condensation reaction of isobutyraldehyde |
| CN114849753A (en) * | 2022-04-26 | 2022-08-05 | 中国科学技术大学 | Preparation method and application of palladium metal cluster catalyst |
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| CN108554432A (en) * | 2018-04-09 | 2018-09-21 | 陕西理工大学 | A kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and preparation method and application |
| CN109833914A (en) * | 2019-03-20 | 2019-06-04 | 河北工业大学 | A kind of palladium catalyst and its preparation method and application of Cu Base Metal organic frame load |
| CN110124722A (en) * | 2019-06-11 | 2019-08-16 | 河北科技大学 | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application |
| CN110404573A (en) * | 2019-06-28 | 2019-11-05 | 中国科学技术大学 | A kind of preparation method and application of extra small palladium-base alloy material |
| CN110711600A (en) * | 2019-10-15 | 2020-01-21 | 兰州大学 | Preparation of metal supported catalyst with nitrogen-doped carbon base derived from bean dregs as carrier and method for catalyzing p-nitrophenol hydrodeoxygenation |
| CN114054045A (en) * | 2021-12-22 | 2022-02-18 | 陕西理工大学 | Preparation method and application of BiOS photocatalyst |
| CN114210327A (en) * | 2021-12-28 | 2022-03-22 | 润泰化学（泰兴）有限公司 | Preparation method of catalyst for preparing isobutyl isobutyrate by adopting Tishchenko condensation reaction of isobutyraldehyde |
| CN114849753A (en) * | 2022-04-26 | 2022-08-05 | 中国科学技术大学 | Preparation method and application of palladium metal cluster catalyst |
| CN114849753B (en) * | 2022-04-26 | 2023-01-17 | 中国科学技术大学 | Preparation method and application of palladium metal cluster catalyst |
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