CN108554432A - A kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and preparation method and application - Google Patents
A kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and preparation method and application Download PDFInfo
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- CN108554432A CN108554432A CN201810312258.3A CN201810312258A CN108554432A CN 108554432 A CN108554432 A CN 108554432A CN 201810312258 A CN201810312258 A CN 201810312258A CN 108554432 A CN108554432 A CN 108554432A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 154
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 77
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 73
- 239000011574 phosphorus Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 44
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019253 formic acid Nutrition 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000012696 Pd precursors Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 235000019441 ethanol Nutrition 0.000 claims description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 235000012245 magnesium oxide Nutrition 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000004675 formic acid derivatives Chemical class 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 150000005041 phenanthrolines Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RWYPDBKDTQPOSR-UHFFFAOYSA-N OC=O.O=C=O Chemical compound OC=O.O=C=O RWYPDBKDTQPOSR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- -1 phosphorus Alkene Chemical class 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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Abstract
The invention discloses nitrogen co-doped graphene-supported palladium-based catalysts of a kind of phosphorus and the preparation method and application thereof.The present invention is by the way that the nitrogen co-doped grapheme material of phosphorus to be add to deionized water, after ultrasonic 5min ~ 30min, the palladium precursor solution that palladium mass concentration is 1% ~ 4.2% is added, obtain raw catalyst, raw catalyst is stirred into 4 ~ 12 h, the sodium borohydride solution of 10ml ~ 20ml molar concentrations 1M/L is added, continues to stir the h of 1h ~ 2, it is filtered, washed, is dried in vacuo, the load capacity for obtaining palladium is the nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus of the wt% of 1.0 wt% ~ 5.0.The catalyst, which can facilitate, to be applied in terms of Catalyzed by Formic Acid decomposing hydrogen-production and formic acid alkali complex catalysts preparation.The present invention is prepared simply, and raw material are easy to get, and gained catalyst is efficient, easy to operate, and repeatable recycling uses, and catalytic activity is unaffected.
Description
Technical field
The invention belongs to catalyst field more particularly to a kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and preparations
Method and application.
Background technology
Carbon-based material is all ideal all the time because it is with high physical and chemical stability, good mechanical stability
Catalyst carrier.In recent years, grapheme material obtains research extensively and concern as the star of carbon material, and tests and manage
By studies have shown that it is heteroatomic doping can be changed grapheme material electronic structure and chemical constitution to improve its electrochemistry
Energy and catalytic performance.Heteroatom doping is carried out to grapheme material, the structure of material can be made to become unordered, to change its mechanics
Property.Heteroatomic introducing can change the local charge density of material, change its catalysis and absorption property, generation is made more to live
Property site, while the defect caused by adulterating can further increase the activity of material.
Compared with the grapheme material of N doping, phosphorus doping can more change the performance of grapheme material, this be because
For the electronegativity of phosphorus（2.19）Than the electronegativity of nitrogen（3.04）It is lower, and the atomic radius of phosphorus atoms is than carbon bigger, it is intended to shape
At the graphene surface of bending, this will generate more active sites.In conjunction with the advantages of two kinds of Heteroatom dopings, there is high activity
Site and the nitrogen co-doped Carbon Materials of defect phosphorus can participate in reacting directly as catalyst, can also be used as the load of metallic catalyst
Body, it can be formed with metallic strong bonded prevents it from reuniting and falling off.
The nitrogen co-doped carbon material preparation method of phosphorus has been a hot spot of research, and main preparation method is fabricated in situ
Method, such as patent（102583312 A of the CN such as Fu Jianwei）It reports and leads under the action of activator by phosphorus source and nitrogen source of polyphosphazene
It crosses polymerization pyrolysismethod and is prepared for the nitrogen co-doped porous carbon material of phosphorus.The nitrogen co-doped porous carbon material of phosphorus prepared by in-situ synthesis
Middle phosphorus, nitrogen are mainly present in the form of structure phosphorus, nitrogen in the skeleton of Carbon Materials, have higher hydrogen storage ability.
In the grapheme material for preparing Heteroatom doping based on the in-situ synthesis reported, stress single atom doped
Investigation of materials, and, especially by prepare phosphorus nitrogen co-doped graphite less for the nitrogen co-doped grapheme material research of phosphorus
Alkene material load catalyst is even more a blank for hydrogenation of carbon dioxide formic acid aspect.
Invention content
The purpose of the present invention is to provide a kind of nitrogen co-doped graphene-supported palladium-based catalysts of phosphorus, it is intended to fill up existing skill
The blank of art.
It is still another object of the present invention to provide the preparation methods of the nitrogen co-doped graphene-supported palladium-based catalyst of above-mentioned phosphorus.
Another object of the present invention is to provide the nitrogen co-doped graphene-supported palladium-based catalysts of above-mentioned phosphorus to be catalyzed respectively
Application in terms of formic acid decomposing hydrogen-production and catalysis preparation first Acid-Base compound.
The invention is realized in this way a kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus, the catalyst nitrogen is with phosphorus
Nitrogen co-doped grapheme material is catalyst carrier；Precious metal palladium form in a manner of high dispersive is carried on carrier, and described is urged
The load capacity of palladium is the wt% of 1.0 wt% ~ 5.0 in agent.
The present invention further discloses the preparation method of the nitrogen co-doped graphene-supported palladium-based catalyst of above-mentioned phosphorus, this method
Include the following steps：
（1）The nitrogen co-doped grapheme material of phosphorus is add to deionized water, after ultrasonic 5min ~ 30min, palladium mass concentration is added
For 1% ~ 4.2% palladium precursor solution, raw catalyst is obtained；The grapheme material, deionized water, the quality volume of palladium
Than for 0.5g：100ml：（10~30）mg；
（2）By step（1）Middle raw catalyst stirs 4 ~ 12 h, and the sodium borohydride of 10ml ~ 20ml molar concentrations 1M/L is added
Solution continues to stir the h of 1h ~ 2, and filtering is washed with deionized water, ethyl alcohol successively, and 80 DEG C of 12 h of vacuum drying obtain high dispersive
The nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus；Wherein, the molar ratio of palladium and sodium borohydride is 1：（20~60）.
Preferably, in step（1）In, the preparation of the nitrogen co-doped graphene of phosphorus includes the following steps：
A, porous magnesia, triphenyl phosphorus and phenanthroline are added in ethyl alcohol, 2 ~ 3h of stirring in water bath at a temperature of 60 ~ 90 DEG C,
Ethyl alcohol is removed through Rotary Evaporators, is calcined in nitrogen atmosphere after obtained solid is ground；Wherein, the porous magnesia, three
Phenyl phosphorus, phenanthroline mass ratio be（2~4）：1：（1~2）；
B, calcined product pickling is removed into masterplate, ethyl alcohol washing, 80 DEG C of 12 h of vacuum drying obtain the nitrogen co-doped graphene material of phosphorus
Material.
Preferably, in step（A）In, the calcination process uses from room temperature degree and is warming up to calcination temperature, the calcining
Heating rate is 2.0 ~ 5.0 DEG C/min, and calcination temperature is 700 ~ 900 DEG C, and calcination time is 2 ~ 4h.
Preferably, in step（B）In, the pickling uses mass concentration to be washed for 5% ~ 20% hydrochloric acid.
The present invention further discloses application of the above-mentioned palladium-based catalyst in terms of being catalyzed formic acid decomposing hydrogen-production.
Preferably, which specifically includes following steps：Palladium-based catalyst is added in formic acid solution, wherein described
The dosage of palladium-based catalyst is the 0.01% ~ 5% of formic acid weight；The formic acid concn is 0.5mol/L ~ 4mol/L.
The present invention further discloses application of the above-mentioned palladium-based catalyst in terms of catalysis prepares first Acid-Base compound.
Preferably, which includes the following steps：
Palladium-based catalyst, water, alkali, carbon dioxide, hydrogen are added in autoclave, 80 DEG C ~ 160 DEG C temperature, 2MPa ~
12h ~ 48h is reacted under 8 MPa pressure, obtains first Acid-Base compound；Wherein,
The dosage of the palladium-based catalyst by addition alkali weight 0.1% ~ 20%；The mass concentration of the alkali in water is
1mol/L~4 mol/L；
The hydrogen and CO2Pressure ratio is（1~3）：1.
Preferably, the alkali is in sodium hydroxide, potassium hydroxide, triethylamine, sodium bicarbonate, saleratus and ammonium hydrogen carbonate
At least one.
The present invention overcomes the deficiencies of the prior art and provide a kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus and its system
Preparation Method and application.The present invention first by be phosphorus source using porous magnesia as masterplate, triphenyl phosphorus, phenanthroline be nitrogen source and
The nitrogen co-doped grapheme material of phosphorus is prepared using high temperature pyrolytic cracking (HTP) in charcoal source, on this basis, recycles immersion reduction method
The nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus is prepared, which can apply respectively decomposes system in catalysis formic acid
In terms of hydrogen and catalysis prepare first Acid-Base compound.
Compared with the prior art the shortcomings that and deficiency, the invention has the advantages that：
（1）The nitrogen co-doped grapheme material preparation condition of phosphorus of the invention is easily-controllable, required raw material sources are extensive, is suitable for scale
Chemical industry produces；
（2）The palladium-based catalyst of the present invention utilizes in preparation process has more absorption in the nitrogen co-doped grapheme material of phosphorus
Site generates stronger interaction with palladium, and the size of palladium particle can be controlled in 2nm or so, palladium base catalysis after in-situ reducing
Agent all has preferable performance, and the stabilization of catalyst in catalysis formic acid decomposes and hydrogenation of carbon dioxide formic acid reacts
Property is good；
（3）The palladium-based catalyst of the present invention has higher phosphorus, nitrogen content and larger specific surface area and Metal Palladium is loading
Measure it is higher under the conditions of still size it is smaller.It is demonstrated experimentally that catalyst of the present invention is being catalyzed after reaction, it only need to be by reaction solution
Filtering can be separated by solid-liquid separation, and catalyst is washed with ethyl alcohol, and drying is i.e. reusable, easy to operate, and activity does not reduce.
Description of the drawings
Fig. 1 is the BET figures of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 2 is the pore size distribution figure of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 3 is the SEM figures of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 4 is the TEM figures of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 5 is the full spectrograms of XPS of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 6 is the XPS swarming fitted figures of the N1s of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 7 is the XPS swarming fitted figures of the P2p of the nitrogen co-doped grapheme material of phosphorus obtained in the embodiment of the present invention 4；
Fig. 8 is the STEM figures of the palladium-based catalyst obtained in the embodiment of the present invention 4.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
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
（1）5.0g porous magnesias, 2.0g triphenyl phosphorus, 3.0g phenanthrolines are taken, is added in 100ml ethyl alcohol, heats 60 DEG C
Stirring 2 hours removes ethyl alcohol with Rotary Evaporators, obtains white solid, be put into quartz boat, be placed in tube furnace after grinding,
600 DEG C of holding 4h are warming up to 2.5 DEG C/min in nitrogen atmosphere, are removed with the dilute hydrochloric acid of mass fraction 8% after being cooled to room temperature
Magnesia, ethyl alcohol washing, 80 DEG C of 12 h of vacuum drying obtain the nitrogen co-doped grapheme material of the powdered phosphorus of black solid 1.
（2）In 250 ml round-bottomed flasks, the nitrogen co-doped grapheme material 1 of 0.5 g phosphorus, 100 ml deionized waters are added,
The PdCl containing 10 mg palladiums is added in ultrasonic vibration 20min2Solution, 20 min of ultrasonic vibration stir 2 h, and 10 ml 1 are added
M/L NaBH4, continue to stir 1 h, cooling, filtering is washed with deionized water, ethyl alcohol successively, 80 DEG C be dried in vacuo 12 h to get
The nitrogen co-doped graphene-supported palladium-based catalyst 1 of phosphorus of high dispersive, the mass fraction of Metal Palladium in the catalyst are 2.0wt %.
（3）The reaction with gas measurement device is added in the nitrogen co-doped graphene-supported palladium-based catalyst 1 of 10.0 mg phosphorus
In bottle, the formic acid solution of 1.0 M/L of 5ml is added, it is 260 h to collect gas 100ml, TOF at 80 DEG C in 10 minutes‒1。
（4）The nitrogen co-doped graphene-supported palladium-based catalyst 1 of 20.0 mg phosphorus is packed into 30ml autoclaves, is added
10.0 ml, 1.0 M/L triethylamine solutions, it is closed, after nitrogen displacement three times, it is filled with 3.0 MPa CO successively2, 3.0 MPa
H2, 24 h are reacted at 80 DEG C, is cooled to room temperature, carefully releases residual gas, and catalyst centrifuges, and the concentration of formates is used
Liquid-phase chromatographic analysis is 0.42 M/L, and selectivity is 100%.
Embodiment 2
（1）5.0g porous magnesias, 2.5g triphenyl phosphorus, 2.5g phenanthrolines are taken, is added in 100ml ethyl alcohol, heats 60 DEG C
Stirring 2 hours removes ethyl alcohol with Rotary Evaporators, obtains white solid, be put into quartz boat, be placed in tube furnace after grinding,
700 DEG C of holding 4h are warming up to 3.0 DEG C/min in nitrogen atmosphere, is cooled to after room temperature and removes magnesia with 8% dilute hydrochloric acid,
Ethyl alcohol washs, and 80 DEG C of 12 h of vacuum drying obtain the nitrogen co-doped grapheme material of the powdered phosphorus of black solid 2.
（2）In 250 ml round-bottomed flasks, the nitrogen co-doped grapheme material 2 of 0.5 g phosphorus, 100 ml deionized waters are added,
The PdCl containing 15 mg palladiums is added in ultrasonic vibration 20min2Solution, 20 min of ultrasonic vibration stir 2 h, and 10 ml 1 are added
M/L NaBH4, continue to stir 1 h, cooling, filtering is washed with deionized water, ethyl alcohol successively, 80 DEG C be dried in vacuo 12 h to get
The nitrogen co-doped graphene-supported palladium-based catalyst 2 of phosphorus of high dispersive, the mass fraction of Metal Palladium in the catalyst are 2.0wt %.
（3）The reaction with gas measurement device is added in the nitrogen co-doped graphene-supported palladium-based catalyst 2 of 10.0 mg phosphorus
In bottle, the formic acid solution of 1.0 M/L of 5ml is added, it is 450 h to collect gas 120ml, TOF at 80 DEG C in 10 minutes‒1。
（4）The nitrogen co-doped graphene-supported palladium-based catalyst 2 of 20.0 mg phosphorus is packed into 30ml autoclaves, is added
10.0 ml, 1.0 M/L potassium hydroxide solutions, it is closed, after nitrogen displacement three times, it is filled with 3.0 MPa CO successively2, 3.0
MPa H2, react 24 h at 80 DEG C, be cooled to room temperature, carefully release residual gas, catalyst centrifuges, formates it is dense
Degree liquid-phase chromatographic analysis is 0.53 M/L, and selectivity is 100%.
Embodiment 3
（1）10.0g porous magnesias, 3.0g triphenyl phosphorus, 3.0g phenanthrolines are taken, is added in 100ml ethyl alcohol, heats 60 DEG C
Stirring 2 hours removes ethyl alcohol with Rotary Evaporators, obtains white solid, be put into quartz boat, be placed in tube furnace after grinding,
800 DEG C of holding 3h are warming up to 4.0 DEG C/min in nitrogen atmosphere, is cooled to after room temperature and removes magnesia with 15% dilute hydrochloric acid,
Ethyl alcohol washs, and 80 DEG C of 12 h of vacuum drying obtain the nitrogen co-doped grapheme material of the powdered phosphorus of black solid 3.
（2）In 250 ml round-bottomed flasks, the nitrogen co-doped grapheme material 3 of 0.5 g phosphorus, 100 ml deionized waters are added,
The PdCl containing 20 mg palladiums is added in ultrasonic vibration 20min2Solution, 20 min of ultrasonic vibration stir 2 h, and 10 ml 1 are added
M/L NaBH4, continue to stir 1 h, cooling, filtering is washed with deionized water, ethyl alcohol successively, 80 DEG C be dried in vacuo 12 h to get
The nitrogen co-doped graphene-supported palladium-based catalyst 3 of phosphorus of high dispersive, the mass fraction of Metal Palladium in the catalyst are 3.0wt %.
（3）The reaction with gas measurement device is added in the nitrogen co-doped graphene-supported palladium-based catalyst 3 of 10.0 mg phosphorus
In bottle, the formic acid solution of 1.0 M/L of 5ml is added, it is 588 h to collect gas 140ml, TOF at 80 DEG C in 5 minutes‒1。
（4）The nitrogen co-doped graphene-supported palladium-based catalyst 3 of 20.0 mg phosphorus is packed into 30ml autoclaves, is added
10.0 ml, 1.0 M/L potassium hydroxide solutions, it is closed, after nitrogen displacement three times, it is filled with 3.0 MPa CO successively2, 3.0
MPa H2, react 24 h at 80 DEG C, be cooled to room temperature, carefully release residual gas, catalyst centrifuges, formates it is dense
Degree liquid-phase chromatographic analysis is 0.68 M/L, and selectivity is 100%.
Embodiment 4
（1）Porous magnesia 10.0g, triphenyl phosphorus 2.0g, phenanthroline 3.0g are taken, is added in 100ml ethyl alcohol, heats 60 DEG C
Stirring 2 hours.Ethyl alcohol is removed with Rotary Evaporators, white solid is obtained, is put into quartz boat, is placed in tube furnace after grinding,
900 DEG C of holding 2h are warming up to 5.0 DEG C/min in nitrogen atmosphere, is cooled to after room temperature and removes magnesia with 15% dilute hydrochloric acid,
Ethyl alcohol washs, and 80 DEG C of 12 h of vacuum drying obtain the nitrogen co-doped grapheme material of the powdered phosphorus of black solid 4.
Performance evaluation is carried out to the nitrogen co-doped grapheme material of phosphorus 4 and can be seen that this from Fig. 1 ~ Fig. 2 as shown in Fig. 1 ~ 7
The specific surface area of the nitrogen co-doped grapheme material of phosphorus 4 is 1484m2/ g, Kong Rongwei 3.36cm3/ g, aperture 8.2nm.From Fig. 3 and
Fig. 4 can be seen that the nitrogen co-doped grapheme material 4 of the phosphorus is lamellar structure, there is the thickness of 2 ~ 3 layer graphenes.It can from Fig. 5 to Fig. 7
To find out that the nitrogen co-doped grapheme material 4 of the phosphorus, can from the fitting of the XPS swarmings of nitrogen containing four kinds of carbon, nitrogen, oxygen, phosphorus elements
Go out the nitrogen there are three types of type, it can be seen that there are two types of the phosphorus of chemical environment from the XPS swarming fitted figures of phosphorus.
（2）In 250 ml round-bottomed flasks, the nitrogen co-doped grapheme material 4 of 0.5 g phosphorus, 100 ml deionized waters are added,
The PdCl containing 30 mg palladiums is added in ultrasonic vibration 20min2Solution, 20 min of ultrasonic vibration stir 2 h, and 10 ml 2 are added
M/L NaBH4, continue to stir 1 h, cooling, filtering is washed with deionized water, ethyl alcohol successively, 80 DEG C be dried in vacuo 12 h to get
The nitrogen co-doped graphene-supported palladium-based catalyst 4 of phosphorus of high dispersive, the mass fraction of Metal Palladium in the catalyst are 4.5wt %.
Graphene-supported palladium-based catalyst 4 nitrogen co-doped to phosphorus carries out STEM analyses, as shown in figure 8, can from Fig. 8
It is 2.3nm to go out Metal Palladium average particle size.
（3）The reaction with gas measurement device is added in the nitrogen co-doped graphene-supported palladium-based catalyst 4 of 10.0 mg phosphorus
In bottle, the formic acid solution of 5 ml, 1.0 M/L is added, it is 560 h to collect gas 200ml, TOF at 80 DEG C in 5 minutes‒1。
（4）The nitrogen co-doped graphene-supported palladium-based catalyst 4 of 20.0 mg phosphorus is packed into 30ml autoclaves, is added
10.0 ml, 1.0 M/L potassium hydroxide solutions, it is closed, after nitrogen displacement three times, it is filled with 3.0 MPa CO successively2, 3.0
MPa H2, react 24 h at 80 DEG C, be cooled to room temperature, carefully release residual gas, catalyst centrifuges, formates it is dense
Degree liquid-phase chromatographic analysis is 0.73 M/L, and selectivity is 100%.Catalyst washs through ethyl alcohol, continues under similarity condition after drying
It uses, a concentration of 0.82 M/L of formates, reuses rear catalyst activity again and still keep, illustrate that catalyst has
Preferable stability.
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
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus, which is characterized in that the catalyst nitrogen is with the nitrogen co-doped stone of phosphorus
Black alkene material is catalyst carrier；Precious metal palladium form in a manner of high dispersive is carried on carrier, and palladium in the catalyst
Load capacity is the wt% of 1.0 wt% ~ 5.0.
2. the preparation method of the nitrogen co-doped graphene-supported palladium-based catalyst of phosphorus described in claim 1, which is characterized in that the party
Method includes the following steps：
（1）The nitrogen co-doped grapheme material of phosphorus is add to deionized water, after ultrasonic 5min ~ 30min, palladium mass concentration is added
For 1% ~ 4.2% palladium precursor solution, raw catalyst is obtained；The grapheme material, deionized water, the quality volume of palladium
Than for 0.5g：100ml：（10~30）mg；
（2）By step（1）Middle raw catalyst stirs 4 ~ 12 h, and the sodium borohydride of 10ml ~ 20ml molar concentrations 1M/L is added
Solution continues to stir the h of 1h ~ 2, is filtered, washed, is dried in vacuo, the nitrogen co-doped graphene-supported palladium base of phosphorus for obtaining high dispersive is urged
Agent；Wherein, the molar ratio of palladium and sodium borohydride is 1：（20~60）.
3. the preparation method of palladium-based catalyst as described in claim 1, which is characterized in that in step（1）In, the phosphorus nitrogen is total
The preparation of doped graphene includes the following steps：
A, porous magnesia, triphenyl phosphorus and phenanthroline are added in ethyl alcohol, 2 ~ 3h of stirring in water bath at a temperature of 60 ~ 90 DEG C,
Ethyl alcohol is removed through Rotary Evaporators, is calcined in nitrogen atmosphere after obtained solid is ground；Wherein, the porous magnesia, three
Phenyl phosphorus, phenanthroline mass ratio be（2~4）：1：（1~2）；
B, calcined product pickling is removed into masterplate, ethyl alcohol washing obtains the nitrogen co-doped grapheme material of phosphorus after vacuum drying.
4. the preparation method of palladium-based catalyst as claimed in claim 2, which is characterized in that in step（A）In, it is described calcined
Cheng Caiyong is warming up to calcination temperature from room temperature degree, and the calcining heating rate is 2.0 ~ 5.0 DEG C/min, and calcination temperature is 700 ~
900 DEG C, calcination time is 2 ~ 4h.
5. the preparation method of palladium-based catalyst as claimed in claim 2, which is characterized in that in step（B）In, the pickling is adopted
The hydrochloric acid for being 5% ~ 20% with mass concentration is washed.
6. application of the palladium-based catalyst described in claim 1 in terms of being catalyzed formic acid decomposing hydrogen-production.
7. application as claimed in claim 6, which is characterized in that the application specifically includes following steps：By palladium-based catalyst plus
Enter into formic acid solution, wherein the dosage of the palladium-based catalyst is the 0.01% ~ 5% of formic acid weight；The formic acid concn is
0.5mol/L~4mol/L。
8. application of the palladium-based catalyst described in claim 1 in terms of catalysis prepares first Acid-Base compound.
9. application as claimed in claim 8, which is characterized in that the application includes the following steps：
Palladium-based catalyst, water, alkali, carbon dioxide, hydrogen are added in autoclave, 80 DEG C ~ 160 DEG C temperature, 2MPa ~
12h ~ 48h is reacted under 8 MPa pressure, obtains first Acid-Base compound；Wherein,
The dosage of the palladium-based catalyst by addition alkali weight 0.1% ~ 20%；The mass concentration of the alkali in water is
1mol/L~4 mol/L；
The hydrogen and CO2Pressure ratio is（1~3）：1.
10. application as claimed in claim 9, which is characterized 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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