CN109529878A - With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase - Google Patents
With the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase Download PDFInfo
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- CN109529878A CN109529878A CN201811586255.5A CN201811586255A CN109529878A CN 109529878 A CN109529878 A CN 109529878A CN 201811586255 A CN201811586255 A CN 201811586255A CN 109529878 A CN109529878 A CN 109529878A
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 108090000698 Formate Dehydrogenases Proteins 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019253 formic acid Nutrition 0.000 claims abstract description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004280 Sodium formate Substances 0.000 claims abstract description 9
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 10
- 238000007357 dehydrogenase reaction Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/60—
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
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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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
Abstract
The invention discloses a kind of methods with AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase, belong to technical field of chemistry and chemical engineering.The AgPd/ porous C exCuyOz nanocatalyst prepared is placed in reactor by the present invention, and reactor is placed in water-bath and rises to certain temperature, and then formic acid and sodium formate mixed liquor are added in reactor and react, and the hydrogen of generation is collected using drainage.Unlike existing catalyst: according to the present invention, the high activity for formate dehydrogenase hydrogen, highly selective, high stability nanocatalyst can be made in the molar ratio for adjusting mole when support precursor cerous nitrate, copper nitrate and the 2-methylimidazole of metal Ag, Pd in catalyst.Formate dehydrogenase reaction is carried out using the catalyst, conversion rate of dehydrogenation and selectivity are 100%, and the TOF value of reaction is greater than 190h‑1, 3h is recycled, the TOF value of reaction is still greater than 185h‑1。
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to be catalyzed with AgPd/ porous C exCuyOz nanocatalyst
The method of formate dehydrogenase.
Background technique
Traditional fossil energy reserves are limited and combustion product causes the environmental problem got worse, find substitution conventional fossil
The new energy of the energy is extremely urgent, wherein Hydrogen Energy is known as the new energy of 21 century clean and effective.But hydrogen has very low body
Product energy density and mass energy density, store safe and efficiently hydrogen become restrict key factor that Hydrogen Energy efficiently utilizes it
One.
For the efficient utilization for realizing hydrogen energy source, developing efficient hydrogen storage material is the key that solve Hydrogen Energy large-scale application.
Moore, G.E.et al. (Journal of physical chemistry, 1962,66 (7): 1241-1244) etc. is ground for the first time
Formate dehydrogenase reaction is studied carefully, which opens research of the formic acid as hydrogen storage material.Li Can etc. (201410789328.6) exists
The play-by-play design of the homogeneous dehydrogenation of formic acid in the patent, the catalyst show formate dehydrogenase reaction excellent
Catalytic performance.But homogeneous catalyst in heavy industrialization application process exist be difficult to the shortcomings that recycling, limit
Its industrial application has been made, the research of formate dehydrogenase heterogeneous catalysis is also further promoted.
Summary of the invention
AgPd/ porous C exCuyOz nano-catalytic is used in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of
The method that agent is catalyzed formate dehydrogenase, realizes first to the AgPd/ porous C exCuyOz nanocatalyst under the conditions of relatively mild
The complete dehydrogenation of acid, and there is good catalytic activity, selectivity and stability.
The technical solution adopted by the present invention to solve the technical problems is as follows.
The AgPd/ porous C exCuyOz nanocatalyst prepared is placed in reactor, reactor is placed in water-bath
30~60 DEG C are risen to, be then 1 by molar ratio: the formic acid and sodium formate mixed liquor of (1.6~4.5) are added in reactor and carry out instead
It answers, obtains hydrogen product；The catalyst and mixed liquor mass ratio is 1: (40~100).
The AgPd/ porous C exCuyOz nanocatalyst includes Ag, Pd and porous C exCuyOz, wherein the source Ag
In silver nitrate, Pd derives from potassium chloropalladate, and porous C exCuyOz forms Ce-Cu- by cerous nitrate, copper nitrate and 2-methylimidazole
MOF roasting is made, and the molar ratio of silver nitrate and potassium chloropalladate is 1: (0.5~0.8)；Silver nitrate and cerous nitrate, copper nitrate, 2- first
The molar ratio of base imidazoles is 1: (1~3): (3~7): (28~35).
The AgPd/ porous C exCuyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, copper nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, at 23~36 DEG C
21~28h of lower stirring, centrifugation obtain Ce-Cu-MOF；
(2) Ce-Cu-MOF is transferred to tube furnace, roasting obtains porous C exCuyOz；
(3) the porous C exCuyOz that roasting obtains is placed in silver nitrate and potassium chloropalladate solution, ammonia is used at -4~2 DEG C
Borane solution restores 3~5h, and centrifugal drying obtains AgPd/ porous C exCuyOz nanocatalyst.
In the preparation step (2) of the AgPd/ porous C exCuyOz nanocatalyst: tube furnace maturing temperature is 500
~540 DEG C, 2.5~4h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 8%~14%.
In the preparation step (3) of the AgPd/ porous C exCuyOz nanocatalyst: ammonia borane concentration be 0.12~
0.36mol/L。
Compared with prior art, the present invention has following technical effect that
1, the present invention uses immersion reduction method synthetic catalyst that is easy to operate, being easy to industrial applications, catalyst carrier
Preparation is presoma using cerous nitrate cheap and easy to get, copper nitrate and 2-methylimidazole, and it is molten to be dissolved in methanol by certain mol proportion
Uniform solution is formed in liquid, reacts certain time under mild reaction conditions, centrifugation obtains Ce-Cu-MOF, by Ce-Cu-MOF
It is transferred to tube furnace, roasting obtains porous C exCuyOz under certain roasting condition and atmosphere, roasting is obtained porous
CexCuyOz is placed in the silver nitrate and potassium chloropalladate solution of definite composition, restores one section using ammonia Borane solution in a mild condition
Time, centrifugal drying obtain the AgPd/ porous C exCuyOz nanocatalyst with high dispersancy nano particle.
2, AgPd/ porous C exCuyOz nanocatalyst prepared by the present invention reacts work with higher to formate dehydrogenase
Property, selectivity and stability.Formate dehydrogenase under temperate condition can be realized using the catalyst, and conversion rate of dehydrogenation and selectivity are
100%, the TOF value of reaction is greater than 190h-1, 3h is recycled, the TOF value of reaction is still greater than 185h-1。
Specific implementation method
The present invention is described in further details below by embodiment.But the example is not constituted to limit of the invention
System.
Embodiment 1
Prepare catalyst process
1mmol cerous nitrate, 3mmol copper nitrate and 28mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 28h at 23 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 500 DEG C
Time 4h, calcination atmosphere 14%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.5mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.12mol/L in 2 DEG C of reduction 5h, that is, make
Catalyst is obtained, AgPd is denoted as0.5/ porous C e1Cu3Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 30 DEG C, formic acid and sodium formate mixed liquor 2g that molar ratio is 1: 4.5 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 190h-1, 3h is recycled, reaction
TOF value is still greater than 185h-1。
Embodiment 2
Prepare catalyst process
3mmol cerous nitrate, 7mmol copper nitrate and 35mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 21h at 36 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 540 DEG C
Time 2.5h, calcination atmosphere 8%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.8mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.36mol/L in -4 DEG C of reduction 5h, that is, make
Catalyst is obtained, AgPd is denoted as0.8/ porous C e3Cu7Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 60 DEG C, formic acid and sodium formate mixed liquor 5g that molar ratio is 1: 1.6 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 280h-1, 3h is recycled, reaction
TOF value is still greater than 275h-1。
Embodiment 3
Prepare catalyst process
2mmol cerous nitrate, 5mmol copper nitrate and 32mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 25h at 28 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 520 DEG C
Time 3h, calcination atmosphere 10%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.6mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.32mol/L in -3 DEG C of reduction 4h, that is, make
Catalyst is obtained, AgPd is denoted as0.6/ porous C e2Cu5Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 50 DEG C, formic acid and sodium formate mixed liquor 4g that molar ratio is 1: 2.5 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 233h-1, 3h is recycled, reaction
TOF value is still greater than 229h-1。
Embodiment 4
Prepare catalyst process
3mmol cerous nitrate, 4mmol copper nitrate and 33mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 26h at 24 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 515 DEG C
Time 2.8h, calcination atmosphere 13%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.7mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.29mol/L in 2 DEG C of reduction 5h, that is, make
Catalyst is obtained, AgPd is denoted as0.7/ porous Ce3Cu4Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 55 DEG C, formic acid and sodium formate mixed liquor 3g that molar ratio is 1: 3.2 is added dropwise thereto, collects reaction gas, is measured after reaction
The selectivity of hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 304h-1, 3h is recycled, reaction
TOF value is still greater than 297h-1。
Embodiment 5
Prepare catalyst process
2mmol cerous nitrate, 7mmol copper nitrate and 28mmol 2-methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 28h at 31 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 505 DEG C
Time 3.5h, calcination atmosphere 8%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.6mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.18mol/L in -1 DEG C of reduction 3.5h, i.e.,
Catalyst is made, is denoted as AgPd0.6/ porous C e2Cu7Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 35 DEG C, formic acid and sodium formate mixed liquor 2.5g that molar ratio is 1: 2.1 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 247h-1, 3h, reaction is recycled
TOF value be still greater than 241h-1。
Embodiment 6
Prepare catalyst process
1mmol cerous nitrate, 4mmol copper nitrate and 33mmol2- methylimidazole are dissolved in and is dissolved in 200mL methanol and is formed
One solution stirs 25h at 27 DEG C, and centrifugation obtains Ce-Cu-MOF, Ce-Cu-MOF is transferred to tube furnace, roasts at 535 DEG C
Time 4h, calcination atmosphere 14%O2/N2, roast and porous C exCuyOz be made, porous C exCuyOz obtained is placed in and is contained
In 1mmol silver nitrate and 0.5mmol potassium chloropalladate solution, using the ammonia Borane solution of 0.36mol/L in -4 DEG C of reduction 4.5h, i.e.,
Catalyst is made, is denoted as AgPd0.5/ porous C e1Cu4Oz nanocatalyst, closed preservation.
Dehydrogenation reaction process
The above-mentioned catalyst of 50mg is filled in tubular reactor, then tubular reactor is placed in water-bath and controls reaction temperature
It is 35 DEG C, formic acid and sodium formate mixed liquor 4.5g that molar ratio is 1: 3.5 is added dropwise thereto, collects reaction gas, is surveyed after reaction
The selectivity for obtaining hydrogen is 100%, and the conversion ratio of formic acid is 100%, and the TOF value of reaction is 212h-1, 3h, reaction is recycled
TOF value be still greater than 206h-1。
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from present inventive concept, several simple deductions and replacement can also be made, all shall be regarded as belonging to the present invention by institute
Claims of submission determine the protection scope of patent.
Claims (3)
1. with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase, it is characterised in that: by what is prepared
AgPd/ porous C exCuyOz nanocatalyst is placed in reactor, and reactor is placed in water-bath and rises to 30~60 DEG C, then will
Molar ratio is 1: the formic acid and sodium formate mixed liquor of (1.6~4.5), which are added in reactor, to be reacted, and hydrogen product is obtained；
The catalyst and mixed liquor mass ratio is 1: (40~100)；
The AgPd/ porous C exCuyOz nanocatalyst includes Ag, Pd and porous C exCuyOz, wherein Ag derives from nitre
Sour silver, Pd derive from potassium chloropalladate, and porous C exCuyOz forms Ce-Cu-MOF by cerous nitrate, copper nitrate and 2-methylimidazole and roasts
It fires, the molar ratio of silver nitrate and potassium chloropalladate is 1: (0.5~0.8)；Silver nitrate and cerous nitrate, copper nitrate, 2- methyl miaow
The molar ratio of azoles is 1: (1~3): (3~7): (28~35)；
The AgPd/ porous C exCuyOz nanocatalyst is through the following steps that prepared:
(1) cerous nitrate, copper nitrate and 2-methylimidazole are dissolved in methanol solution and form uniform solution, stirred at 23~36 DEG C
21~28h is mixed, centrifugation obtains Ce-Cu-MOF；
(2) Ce-Cu-MOF is transferred to tube furnace, roasting obtains porous C exCuyOz；
(3) the porous C exCuyOz that roasting obtains is placed in silver nitrate and potassium chloropalladate solution, ammonia borine is used at -4~2 DEG C
3~5h of solution reduction, centrifugal drying obtain AgPd/ porous C exCuyOz nanocatalyst.
2. as described in claim 1 with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase, feature
Be, in the preparation step (2) of the AgPd/ porous C exCuyOz nanocatalyst: tube furnace maturing temperature be 500~
540 DEG C, 2.5~4h of calcining time, calcination atmosphere O2/N2, wherein O2Volume accounting be 8%~14%.
3. as described in claim 1 with the method for AgPd/ porous C exCuyOz nanocatalyst catalysis formate dehydrogenase, feature
Be, in the preparation step (3) of the AgPd/ porous C exCuyOz nanocatalyst: ammonia borane concentration be 0.12~
0.36mol/L。
Priority Applications (1)
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