CN108816289A - The preparation method and application of the CrPd nanocatalyst of the MOFs load of amino functional - Google Patents
The preparation method and application of the CrPd nanocatalyst of the MOFs load of amino functional Download PDFInfo
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- 101100116973 Mus musculus Dmbt1 gene Proteins 0.000 title claims abstract description 77
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 49
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013177 MIL-101 Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 21
- 235000019253 formic acid Nutrition 0.000 abstract description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000011232 storage material Substances 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 108090000698 Formate Dehydrogenases Proteins 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007357 dehydrogenase reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention discloses a kind of preparation method and applications of the CrPd nanocatalyst of the MOFs of amino functional load, include the following steps：MIL-101 is prepared by hydro-thermal method；MIL-101-NH is prepared by rear modification method2；CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst.The present invention can be used as a kind of novel, simple and direct, efficient method, to synthesize loaded palladium-based catalyst, synthesized catalyst is applied in the reaction of formic acid (FA) decomposing hydrogen-production, extraordinary catalytic activity can be obtained, this provides new approach to develop safe and efficient solid catalyst, and further promotes application of the FA as hydrogen storage material in on-vehicle fuel.
Description
Technical field
The present invention relates to catalysis and the sustainable development field of the energy, what the MOFs of especially a kind of amino functional was loaded
The preparation method and application of CrPd nanocatalyst.
Background technique
The energy is the key that the mankind depend on for existence and development, and with the rapid development of society, fossil fuel constantly reduces band
The energy crisis and its environmental pollution of combustion product bring come constantly propose the energy system at present based on fossil fuel
Severe challenge.Develop the inexorable trend that novel renewable and clean energy resource is energy field development.Hydrogen Energy as it is a kind of cleaning,
Safe and efficient ideal secondary energy sources are favored by people.Using hydrogen as the fuel cell of hydrogen source be widely used in it is small-sized just
Take the fields such as formula product, fuel cell car, aerospace.However, the hydrogen of low-density is not easy to store and transport, to make
The about development of fuel cell.Compared with traditional high-pressure gaseous hydrogen storage and low temperature liquid hydrogen storage, hydrogen storage material hydrogen storage while reality
High storage density and high safety are showed.Formic acid (HCOOH, FA) is used as a kind of lightweight small-molecule chemical hydrogen storage material, tool
There is higher energy density, be at room temperature stable liquid, easily fills, it is considered to be a kind of change with huge applications potentiality
Learn hydrogen storage material.Under the action of catalyst, formic acid by dehydrogenation reaction, can generate the hydrogen and carbon dioxide (HCOOH of needs
→H2+CO2)；It is also possible to generate water and carbon monoxide (HCOOH → H by dehydration2O+CO).Wherein formate dehydrogenase reacts
Be it is intended that path because formic acid dehydration generate CO easily make catalyst poisoning and inactivate, must strictly control
The generation of formic acid dehydration processed.
Currently, the catalyst for the reaction of formic acid decomposing hydrogen-production mainly has homogeneous catalyst and heterogeneous catalyst, wherein more
Phase catalyst is since it has many advantages, such as to be easy to control, is extensively studied and uses convenient for recycling.In formate dehydrogenase reaction,
Noble metal (such as Pd, Au) nano material is to the hydrogen production reaction of FA catalytic activity with higher, it is contemplated that noble metal is limited
Resource and expensive price, replace noble metal that can reduce catalyst cost using base metal part；Binary or three simultaneously
Synergistic effect in first nanostructured materials catalyst between two or three of metal can effectively improve reactivity.However it is big at present
Catalytic performance of the majority containing non-noble metal FA catalyst for hydrogen does not reach and actually answers there are still very big room for promotion
It is required that.
In addition, the catalytic performance of metal nano material with its element composition in addition to having outside the Pass, it is also big with its dispersion degree, particle
Small, specific surface area and characteristic electron close relation.Due to high surface energy nanoscale metallic particles during the reaction
It is easy to reunite, lead to the reduction of reactivity site concentration, this largely constrains its catalytic performance, therefore to obtain partial size
Nanocatalyst uniformly tiny, dispersibility is high selects catalyst carrier appropriate to become a kind of effective method.With it is all
Multichip carrier material is compared, and metal organic framework (MOFs) is used as a kind of Porous coordination polymer, has high-specific surface area and chemistry
The advantages that coordinability, and be easy to carry out functional modification by the methods of post-processing or ligand design.After modification
MOFs passes through the interaction of functionalization group and metal nano catalyst, can be further improved point of metal nano catalyst
Property is dissipated, while improving its electronic structure, to improve the catalytic performance of functionalization MOFs base complex.
In conclusion finding a kind of simple and efficient way synthesizing efficient, highly selective, inexpensive and good dispersion
Loaded heterogeneous catalyst is very important for improving FA dehydrogenation reaction efficiency.
Summary of the invention
The invention aims to solve the deficiencies in the prior art, a kind of MOFs load of amino functional is provided
CrPd nanocatalyst preparation method and application.
In order to achieve the above objectives, the present invention is implemented according to following technical scheme：
The preparation method of the CrPd nanocatalyst of the MOFs load of amino functional, includes the following steps：
S1, MIL-101 is prepared by hydro-thermal method；
S2, method preparation MIL-101-NH is modified after passing through using MIL-101 obtained2；
S3, MIL-101-NH obtained is used2CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst.
Further, the S1 the specific steps are：
S11, the HF of the 0.3mL of 40wt% is added in 28.8mL deionized water, is stirred evenly；It is 1 by molar ratio:1
C8H6O4With Cr (NO3)3·9H2O is evenly spread in above-mentioned solution, then is put it into reaction kettle, heats 8h at 473K,
Cooled to room temperature；
S12, obtained product dissolve in the NH that concentration is 1M after being cleaned several times with ethyl alcohol4In F aqueous solution, at 343K
It impregnates for 24 hours, the solution after immersion is finally dried overnight in the vacuum environment under 423K by being centrifuged repeatedly, washing, and obtains green
The MIL-101 of color.
Further, the S2 the specific steps are：
S21,100mg MIL-101 is added to 5mL HNO first3With 7mL H2SO4Mixed solution in, under ice bath
5h is stirred, then 50mL ice cube is added in above-mentioned solution, is washed by 2 washings and 2 ethyl alcohol, MIL-101-NO is obtained2；
S22, secondly by 3.26g SnCl2With 100mg MIL-101-NO2It is added in 20mL ethyl alcohol, is stirred at 343K
6h, obtained solid state powder is added to 20~30min of ultrasound in HCl solution after being centrifuged, by filtering, repeatedly wash and
Ethyl alcohol is washed, and dried overnight under the vacuum environment of 423K, obtains the MIL-101-NH of yellow green2。
Further, the S3 the specific steps are：
S31, by 40mg MIL-101-NH2It is dissolved into 10mL deionized water, ultrasonic 40min obtains solution A；
S32, by molar ratio be 1:2 PdCl2It is dissolved in distilled water with NaCl, is uniformly mixing to obtain the concentration of brown color
For the Na of 0.025M2PdCl4Aqueous solution；Take the Na of 0.06mmol2PdCl4Cr (the NO of aqueous solution and 0.04mmol3)3·9H2O adds
Enter into solution A, stir 2h at room temperature, obtains mixed solution B；
S33, by 30~50mg NaBH4It is added in mixed solution B as reducing agent, continues stirring reduction, mixed
Solution C；
S34, at room temperature, by above-mentioned mixed solution C, magnetic agitation is restored in air, when there is no bubble, 8000~
12000rpm is centrifuged 3~10min, washes 3 times, obtains CrPd/MIL-101-NH2Nanocatalyst.
Further, NaBH is used in the S334The temperature restored is room temperature, and the recovery time is 10~30min.
Further, CrPd/MIL-101-NH obtained in the S342In nanocatalyst, bianry alloy CrPd nanometers
Grain (NPs) is in MIL-101-NH2It is uniformly distributed in skeleton, and particle size is 2.5~3.0nm.
In addition, the purposes of the CrPd nanocatalyst of the MOFs load of the amino functional produced by the present invention, is used
In catalysis FA solution decomposing hydrogen-production reaction, specifically according to CrPd/MIL-101-NH2The molar ratio of nanocatalyst and FA is
0.02 is mixed, and wherein the concentration of FA solution is that 1M can produce 225mL gas at 323K in 7.5 minutes, initial to turn
Changing frequency (TOF) isConversion ratio is 100%；Hydrogen selective is 100%.
Compared with prior art, the present invention uses the MIL-101 of impregnation-reduction method success synthesizing amino functionalization negative first
CrPd NPs is carried, can be completed at room temperature, have many advantages, such as synthesis process quickly and efficiently, it is easy to operate, and significantly improve
CrPd NPs is in MIL-101-NH2Dispersibility on substrate and the particle size for reducing metal NPs；By the CrPd/ of synthesis
MIL-101-NH2Nanocatalyst is applied to catalysis FA aqueous solution decomposing hydrogen-production reaction, and the catalyst is in no any additive
Excellent catalytic performance still is shown under the conditions of existing, at 323K, can produce 225mL gas in 7.5 minutes, initially
Transformation frequency (TOF) isConversion ratio is 100%；Hydrogen selective is 100%.Using
On the one hand the MOFs of amino functional effectively inhibits the reunion of catalyst activity component CrPd NPs as substrate, obtain
Even tiny metal NPs, to obtain the reactivity site of high concentration；Another aspect functionalization group-NH2In the height that contains
Concentration pyridine N can provide more electronics for catalyst activity atom, so that the catalyst activity for obtaining high electron density is former
Son, and then it has been obviously improved the activity of catalyst.
Summary, the present invention can be used as a kind of novel, simple and direct, efficient method, to synthesize loaded palladium-based catalyst,
By synthesized catalyst be applied to FA decomposing hydrogen-production reaction in, extraordinary catalytic activity can be obtained, this for development safety,
Efficient solid catalyst provides new approach, and further promote FA as hydrogen storage material answering in on-vehicle fuel
With.
Detailed description of the invention
Fig. 1 is CrPd/MIL-101-NH in embodiment 12Under (a) low power of nanocatalyst, (b) the transmission electricity under high power
Sub- microscope figure, wherein：Illustration is the particle diameter distribution histogram of CrPd nano particle.It (c) is CrPd/MIL-101 in comparative example 1
And CrPd/MIL-101-NH in embodiment 12X-ray diffraction spectrogram；
Fig. 2 (a) is CrPd/MIL-101-NH in embodiment 12The x-ray photoelectron spectroscopy figure of the N 1s of catalyst；(b)
For CrPd/MIL-101-NH in CrPd, CrPd/MIL-101 in comparative example 1 and embodiment 12Pd 3d x-ray photoelectron energy
Spectrogram；
Fig. 3 (a) is CrPd/MIL-101-NH in embodiment 12And in comparative example 1 CrPd, CrPd/MIL-101 catalyst
FA aqueous solution hydrogen manufacturing curve graph is catalyzed at 323K, (b) the initial conversion frequency reacted for the corresponding catalysis of three kinds of catalyst of (a)
Rate is (c) CrPd/MIL-101-NH in comparative example 22It is catalyzed FA aqueous solution hydrogen manufacturing curve graph at different temperatures, (d) being will
(c) CrPd/MIL-101-NH that the data in are fitted2The Arrhenius of catalyst FA decomposing hydrogen-production reaction is bent
Line.
Fig. 4 is the transmission electron microscope picture of catalyst prepared by comparative example 1.
Specific embodiment
The invention will be further described combined with specific embodiments below, in the illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
The preparation method of the CrPd nanocatalyst of the MOFs load of amino functional, includes the following steps：
S1, MIL-101 is prepared by hydro-thermal method：
S11, the HF of the 0.3mL of 40wt% is added in 28.8mL deionized water, is stirred evenly；It is 1 by molar ratio:1
C8H6O4With Cr (NO3)3·9H2O is evenly spread in above-mentioned solution, then is put it into reaction kettle, heats 8h at 473K,
Cooled to room temperature；
S12, obtained product dissolve in the NH that concentration is 1M after being cleaned several times with ethyl alcohol4In F aqueous solution, at 343K
It impregnates for 24 hours, the solution after immersion is finally dried overnight in the vacuum environment under 423K by being centrifuged repeatedly, washing, and obtains green
The MIL-101 of color；
S2, method preparation MIL-101-NH is modified after passing through using MIL-101 obtained2：
S21,100mg MIL-101 is added to 5mL HNO first3With 7mL H2SO4Mixed solution in, under ice bath
5h is stirred, then 50mL ice cube is added in above-mentioned solution, is washed by 2 washings and 2 ethyl alcohol, MIL-101-NO is obtained2；
S22, secondly by 3.26g SnCl2With 100mg MIL-101-NO2It is added in 20mL ethyl alcohol, is stirred at 343K
6h, the solid state powder obtained after centrifugation are added to ultrasound 20min in HCl solution, by filtering, repeatedly washing and ethyl alcohol
It washes, and dried overnight under the vacuum environment of 423K, obtains the MIL-101-NH of yellow green2；
S3, MIL-101-NH obtained is used2CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst：
S31, by 40mg MIL-101-NH2It is dissolved into 10mL deionized water, ultrasonic 40min obtains solution A；
S32, by molar ratio be 1:2 PdCl2It is dissolved in distilled water with NaCl, is uniformly mixing to obtain the concentration of brown color
For the Na of 0.025M2PdCl4Aqueous solution；Take the Na of 0.06mmol2PdCl4Cr (the NO of aqueous solution and 0.04mmol3)3·9H2O adds
Enter into solution A, stir 2h at room temperature, obtains mixed solution B；
S33, by 50mg NaBH4It is added in mixed solution B as reducing agent, continues to stir at room temperature, obtain mixing molten
Liquid C；
S34, at room temperature, by above-mentioned mixed solution C, magnetic agitation is restored in air, when there is no bubble, 8000rpm
It is centrifuged 3min, washes 3 times, obtains CrPd/MIL-101-NH2Nanocatalyst.
Embodiment 2
The preparation method of the CrPd nanocatalyst of the MOFs load of amino functional, includes the following steps：
S1, MIL-101 is prepared by hydro-thermal method：
S11, the HF of the 0.3mL of 40wt% is added in 28.8mL deionized water, is stirred evenly；It is 1 by molar ratio:1
C8H6O4With Cr (NO3)3·9H2O is evenly spread in above-mentioned solution, then is put it into reaction kettle, heats 8h at 473K,
Cooled to room temperature；
S12, obtained product dissolve in the NH that concentration is 1M after being cleaned several times with ethyl alcohol4In F aqueous solution, at 343K
It impregnates for 24 hours, the solution after immersion is finally dried overnight in the vacuum environment under 423K by being centrifuged repeatedly, washing, and obtains green
The MIL-101 of color；
S2, method preparation MIL-101-NH is modified after passing through using MIL-101 obtained2：
S21,100mg MIL-101 is added to 5mL HNO first3With 7mL H2SO4Mixed solution in, under ice bath
5h is stirred, then 50mL ice cube is added in above-mentioned solution, is washed by 2 washings and 2 ethyl alcohol, MIL-101-NO is obtained2；
S22, secondly by 3.26g SnCl2With 100mg MIL-101-NO2It is added in 20mL ethyl alcohol, is stirred at 343K
6h, the solid state powder obtained after centrifugation are added to ultrasound 30min in HCl solution, by filtering, repeatedly washing and ethyl alcohol
It washes, and dried overnight under the vacuum environment of 423K, obtains the MIL-101-NH of yellow green2；
S3, MIL-101-NH obtained is used2CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst：
S31, by 40mg MIL-101-NH2It is dissolved into 10mL deionized water, ultrasonic 40min obtains solution A；
S32, by molar ratio be 1:2 PdCl2It is dissolved in distilled water with NaCl, is uniformly mixing to obtain the concentration of brown color
For the Na of 0.025M2PdCl4Aqueous solution；Take the Na of 0.06mmol2PdCl4Cr (the NO of aqueous solution and 0.04mmol3)3·9H2O adds
Enter into solution A, stir 2h at room temperature, obtains mixed solution B；
S33, by 50mg NaBH4It is added in mixed solution B as reducing agent, continues to stir at room temperature, obtain mixing molten
Liquid C；
S34, at room temperature, by above-mentioned mixed solution C, magnetic agitation is restored in air, when there is no bubble,
12000rpm is centrifuged 10min, washes 3 times, obtains CrPd/MIL-101-NH2Nanocatalyst.
Embodiment 3
The preparation method of the CrPd nanocatalyst of the MOFs load of amino functional, includes the following steps：
S1, MIL-101 is prepared by hydro-thermal method：
S11, the HF of the 0.3mL of 40wt% is added in 28.8mL deionized water, is stirred evenly；It is 1 by molar ratio:1
C8H6O4With Cr (NO3)3·9H2O is evenly spread in above-mentioned solution, then is put it into reaction kettle, heats 8h at 473K,
Cooled to room temperature；
S12, obtained product dissolve in the NH that concentration is 1M after being cleaned several times with ethyl alcohol4In F aqueous solution, at 343K
It impregnates for 24 hours, the solution after immersion is finally dried overnight in the vacuum environment under 423K by being centrifuged repeatedly, washing, and obtains green
The MIL-101 of color；
S2, method preparation MIL-101-NH is modified after passing through using MIL-101 obtained2：
S21,100mg MIL-101 is added to 5mL HNO first3With 7mL H2SO4Mixed solution in, under ice bath
5h is stirred, then 50mL ice cube is added in above-mentioned solution, is washed by 2 washings and 2 ethyl alcohol, MIL-101-NO is obtained2；
S22, secondly by 3.26g SnCl2With 100mg MIL-101-NO2It is added in 20mL ethyl alcohol, is stirred at 343K
6h, the solid state powder obtained after centrifugation are added to ultrasound 25min in HCl solution, by filtering, repeatedly washing and ethyl alcohol
It washes, and dried overnight under the vacuum environment of 423K, obtains the MIL-101-NH of yellow green2；
S3, MIL-101-NH obtained is used2CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst：
S31, by 40mg MIL-101-NH2It is dissolved into 10mL deionized water, ultrasonic 40min obtains solution A；
S32, by molar ratio be 1:2 PdCl2It is dissolved in distilled water with NaCl, is uniformly mixing to obtain the concentration of brown color
For the Na of 0.025M2PdCl4Aqueous solution；Take the Na of 0.06mmol2PdCl4Cr (the NO of aqueous solution and 0.04mmol3)3·9H2O adds
Enter into solution A, stir 2h at room temperature, obtains mixed solution B；
S33, by 40mg NaBH4It is added in mixed solution B as reducing agent, continues to stir at room temperature, obtain mixing molten
Liquid C；
S34, at room temperature, by above-mentioned mixed solution C, magnetic agitation is restored in air, when there is no bubble,
10000rpm is centrifuged 8min, washes 3 times, obtains CrPd/MIL-101-NH2Nanocatalyst.
Sample detection
By CrPd/MIL-101-NH made from embodiment 12Nanocatalyst, which is dissolved into appropriate amount of deionized water, to be diluted, and is surpassed
Sound is uniformly dispersed, and the solution after taking 1-2 drop to dilute drips on copper mesh, carries out transmission electron microscope (TEM) observation analysis.Again will
Aforementioned CrPd/MIL-101-NH obtained2Catalyst vacuum drying carries out X-ray powder diffraction (XRD) analysis, with reference to Fig. 1,
Analysis the result shows that, which has successfully synthesized MIL-101-NH2The CrPd bianry alloy catalyst of load, CrPd
NPs is dispersed in MIL-101-NH2In skeleton, and particle size is about 2.5~3.0nm.In addition, by made from embodiment 1
CrPd/MIL-101-NH2Nanocatalyst vacuum drying, the powder after taking appropriate drying carry out x-ray photoelectron spectroscopy (XPS)
Detection, with reference to Fig. 2, testing result is shown, CrPd/MIL-101-NH2Sample surfaces pyridine N accounting 72.93% in N element；
It is compared with CrPd, CrPd/MIL-101, functionalization group-NH2Incorporation, cause the electron density of Pd to increase.
By CrPd/MIL-101-NH made from embodiment 12Nanocatalyst is for being catalyzed the reaction of FA solution decomposing hydrogen-production：
By CrPd/MIL-101-NH2The molar ratio of catalyst and FA are mixed for 0.02, and wherein the concentration of FA solution is 1M, and is led to
It crosses gas burette and measures generated gas, at 323K, CrPd/MIL-101-NH2Nanocatalyst is catalyzed FA aqueous solution system
Shown in (a) in the gas production (mL) and time (min) of hydrogen process such as Fig. 3, catalysis FA decomposing hydrogen-production can be in 7.5 minutes
Gas production reaches 225mL, and initial conversion frequency (TOF) is(as shown in Figure 3b), conversion
Rate reaches 100%.
Comparative example 1
MIL-101 is prepared with hydro-thermal method, by the Cr (NO of 0.04mmol3)3With the Na of 0.06mmol2PdCl4Be dissolved in containing
In the aqueous solution of 40mg MIL-101, stir evenly；The NaBH of 40mg4It is added in above-mentioned solution, at 25 DEG C, magnetic agitation
To complete reduction；After washing, CrPd/MIL-101 nanocatalyst is made in centrifugation.By the Cr (NO of 0.04mmol3)3With
The Na of 0.06mmol2PdCl4It is dissolved in suitable deionized water, the NaBH of 40mg4It is added in above-mentioned solution, at 25 DEG C,
Magnetic agitation is restored to complete；After washing, CrPd catalyst is made in centrifugation.
Above-mentioned CrPd/MIL-101 nanocatalyst and CrPd catalyst are distributed in water, the FA of 5mmol is added, and
Generated gas flow is measured by gas burette.At 323K, CrPd/MIL-101 nanocatalyst and CrPd catalyst are urged
Change shown in (a) in the gas production (mL) and time (min) such as Fig. 3 of FA hydrogen production process, is catalyzed the initial conversion of FA hydrolytic hydrogen production
Frequency (TOF) is respectively (as shown in Figure 3b).
Comparative example 2
MIL-101 is prepared with hydro-thermal method, method is modified after and prepares MIL-101-NH2, by the Cr (NO of 0.04mmol3)3With
The Na of 0.06mmol2PdCl4It is dissolved in containing 40mg MIL-101-NH2Aqueous solution in, stir evenly；The NaBH of 40mg4Add
Enter into above-mentioned solution, at 25 DEG C, magnetic agitation to complete reduction；After washing, CrPd/MIL-101-NH is made in centrifugation2It receives
Rice catalyst.
By CrPd/MIL-101-NH2Nanocatalyst is distributed in water, adds the formic acid of 5mmol, and passes through gas flow
Pipe measures generated hydrogen.Change reaction temperature, records the CrPd/MIL-101-NH under 303,313,323 and 333K respectively2
Nanocatalyst is catalyzed the gas production (mL) of FA hydrogen production process and the relationship of time (min), draws as shown in (c) in Fig. 3, will
Data in Fig. 3 c are fitted to obtain CrPd/MIL-101-NH2Catalysis FA decomposing hydrogen-production Activation energy is 43.5kJ/mol (as schemed
Shown in 3d).
Fig. 4 is the TEM photo of CrPd/MIL-101 and CrPd nanocatalyst made from comparative example 1, (a) CrPd/MIL-
101, (b) CrPd.It is distributed in it can be seen from the figure that CrPdNPs is more uniform in CrPd/MIL-101 nanocatalyst
On MIL-101 carrier, average particle size particle size is about 9.5-10nm, and distribution of particles is sparse；And then occur in CrPd NPs
Apparent agglomeration.
Summary, the present invention uses the MIL-101 load C rPdNPs of impregnation-reduction method success synthesizing amino functionalization, in room
It can be completed under temperature, have many advantages, such as synthesis process quickly and efficiently, it is easy to operate, and CrPd NPs is significantly improved in MIL-
101-NH2Dispersibility on substrate and the particle size for reducing metal NPs；By the CrPd/MIL-101-NH of synthesis2Nanometer is urged
Agent is applied to catalysis FA aqueous solution decomposing hydrogen-production reaction, and remain unchanged table under the conditions of the catalyst is existing for no any additive
Reveal excellent catalytic performance, at 323K, can produce 225mL gas in 7.5 minutes, initial conversion frequency (TOF) is Conversion ratio is 100%；Hydrogen selective is 100%.Made using the MOFs of amino functional
For substrate, the reunion of catalyst activity component CrPd NPs is on the one hand effectively inhibited, obtains uniformly tiny metal NPs, from
And obtain the reactivity site of high concentration；Another aspect functionalization group-NH2In the high-purity pyridine N that contains can be to urge
Agent active atomic provides more electronics, to obtain the catalyst activity atom of high electron density, and then is obviously improved
The activity of catalyst.
The limitation that technical solution of the present invention is not limited to the above specific embodiments, it is all to do according to the technique and scheme of the present invention
Technology deformation out, falls within the scope of protection of the present invention.
Claims (8)
1. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional is loaded, which is characterized in that include the following steps：
S1, MIL-101 is prepared by hydro-thermal method；
S2, method preparation MIL-101-NH is modified after passing through using MIL-101 obtained2；
S3, MIL-101-NH obtained is used2CrPd/MIL-101-NH is prepared by impregnation-reduction method2Nanocatalyst.
2. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional according to claim 1 is loaded, special
Sign is, the S1 the specific steps are：
S11, the HF of the 0.3mL of 40wt% is added in 28.8mL deionized water, is stirred evenly；It is 1 by molar ratio:1
C8H6O4With Cr (NO3)3·9H2O is evenly spread in above-mentioned solution, then is put it into reaction kettle, heats 8h at 473K, from
So it is cooled to room temperature；
S12, obtained product dissolve in the NH that concentration is 1M after being cleaned several times with ethyl alcohol4In F aqueous solution, impregnated at 343K
For 24 hours, the solution after immersion is finally dried overnight in the vacuum environment under 423K by being centrifuged repeatedly, washing, and obtains green
MIL-101。
3. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional according to claim 1 is loaded, special
Sign is, the S2 the specific steps are：
S21,100mg MIL-101 is added to 5mL HNO first3With 7mL H2SO4Mixed solution in, stirred under ice bath
5h, then 50mL ice cube is added in above-mentioned solution, it is washed by 2 washings and 2 ethyl alcohol, obtains MIL-101-NO2；
S22, secondly by 3.26g SnCl2With 100mg MIL-101-NO2It is added in 20mL ethyl alcohol, 6h is stirred at 343K, pass through
It crosses the solid state powder obtained after centrifugation and is added to 20~30min of ultrasound in HCl solution, by filtering, repeatedly washing and ethyl alcohol
It washes, and dried overnight under the vacuum environment of 423K, obtains the MIL-101-NH of yellow green2。
4. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional according to claim 1 is loaded, special
Sign is：The S3 the specific steps are：
S31, by 40mg MIL-101-NH2It is dissolved into 10mL deionized water, ultrasonic 40min obtains solution A；
S32, by molar ratio be 1:2 PdCl2It is dissolved in distilled water with NaCl, the concentration for being uniformly mixing to obtain brown color is
The Na of 0.025M2PdCl4Aqueous solution；Take the Na of 0.06mmol2PdCl4Cr (the NO of aqueous solution and 0.04mmol3)3·9H2O is added
Into solution A, 2h is stirred at room temperature, obtains mixed solution B；
S33, by 30~50mg NaBH4It is added in mixed solution B as reducing agent, continues stirring reduction, obtain mixed solution
C；
S34, at room temperature, by above-mentioned mixed solution C, magnetic agitation is restored in air, when there is no bubble, 8000~
12000rpm is centrifuged 3~10min, washes 3 times, obtains CrPd/MIL-101-NH2Nanocatalyst.
5. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional according to claim 4 is loaded, special
Sign is：NaBH is used in the S334The temperature restored is room temperature, and the recovery time is 10~30min.
6. the preparation method for the CrPd nanocatalyst that the MOFs of amino functional according to claim 4 is loaded, special
Sign is：CrPd/MIL-101-NH obtained in the S342In nanocatalyst, bianry alloy CrPd nano particle (NPs)
In MIL-101-NH2It is uniformly distributed in skeleton, and particle size is 2.5~3.0nm.
7. the application for the CrPd nanocatalyst that the MOFs of the amino functional as described in claim 1-6 is any is loaded, special
Sign is：For being catalyzed the reaction of FA solution decomposing hydrogen-production.
8. the application for the CrPd nanocatalyst that the MOFs of amino functional according to claim 7 is loaded, feature exist
In, the specific steps are：According to CrPd/MIL-101-NH2The molar ratio of nanocatalyst and FA are mixed for 0.02, wherein FA
The concentration of solution is 1M.
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